Birla Institute of Technology & Science, Pilani, Rajasthan - 333 031

IInd Semester 2015-2016

CHEM F342 ORGANIC CHEMISTRY IV
Comprehensive Examination (Open Book)
Max. Marks: 60 Duration: 120 minutes Date: 11th May 2016
Write your name and ID no on the question papers. All questions are compulsory.
Q.1 (i) Eletriptan, is an antimigrane drug that has been recently developed. Design the synthesis of Eletriptan (with
detailed mechanism), starting from appropriate A and B (hint given below). [5]

(ii) Apomorphine dimethyl ether, a drug used in the treatment of Parkinson's disease, could be obtained from intermediate
J in a series of steps. Work out the synthesis of intermediate J with detailed mechanism. [5]

Q.2 (i) A 3,8-dialkylphenantroline based hydrogenating catalyst could be synthesized by a popular name reaction from
synthetic equivalents C and D (see Figure below). Intermediate C itself could be prepared by the same reaction between E
and D, followed by reduction. Identify C, D and E and design the synthesis of C (with detailed mechanism) starting from
E and D. [5]

(ii) Identify the final product for the following chemical transformations (No mechanism) [1x2=2]

(iii) Work out a detailed mechanism for the following chemical transformation and identify the product. [3]

....................................................................................................................................................................................
P.T.O Page 1
Q3. (i) State two crucial challenges in planning a chemical synthesis of prostaglandins. [2]
(ii) Prostaglandin E1 can be synthesized starting from acyclic -ketoacid precursor as shown below. Complete the missing
products/reagents shown in the following synthetic sequence: [5]

(iii) Write down the structure of the following fatty acid: 20:3 (  

Q (i) An unknown alkaloid C17H21O4N2 undergoes the following tests: It gives off 44.8 litres of CH 4 gas (at STP) when
treated with MeMgI. When treated with HI it forms 1 mol of AgI ppt while on treatment with HCl, 1 mol of formaldehyde
is formed. It reacts with nitrous acid to form one mol of nitroso oil derivative. It requires three Hofmann degradations to
form the corresponding alkene derivative. Clearly show which structural feature of the alkaloid is responsible for which
test. Finally give an acceptable structure of this tetracyclic alkaloid. [5]
(ii) Cocaine is extracted from the leaves of Erythroxylon coca whose main constituent is shown below. How will you
convert this raw material to Ecgonine and then to cocaine in three simple steps. [3]

(iii) Coniine is usually concealed by simple chemical procedure, transported, and then finally freebased at the site of use.
Explain the reaction involved in concealment and freebasing of coniine by simple equations. [2]

Q5. (i) Show the H-binding interactions present in the -sheet of Gly-Ala-Val structure. [2]
(ii) Complete the following reaction sequence showing the structures in each step. [8]

Q6. (i) For Vitamin A structure determination: Show the important reactions and the structural information provided by
each reaction in determining the structure of Vitamin A. [6]
(ii) Show by equations how you will prepare the thiazole part of the vitamin Thiamine. Also show how this thiazole part is
coupled with the pyrimidine part to form Thiamine hydrochloride salt. [4]
....................................................................................................................................................................................
END Page 2
 Birla Institute of Technology & Science, Pilani, Rajasthan - 333 031 SET X
II Semester 2015-2016
nd

CHEM F342 ORGANIC CHEMISTRY IV

Comprehensive Examination (Closed Book)
Max. Marks: 30 Duration: 60 minutes Date: 11th May 2016
NOTE: There are THIRTY questions in all. Attempt all the questions. Indicate the most appropriate answer
by entering A, B, C or D in boxes provided in the front of each question. Do not overwrite. Each question
carries one mark. Part II may be collected after submitting Part I.

Q. 01. The correct structure of 6H-1,3-thiazine is

Q. 02. Which of the following compounds is least basic ?

Q. 03. Which one of the following products is obtained by the reaction between 2-phenyloxetane and HCN ?

Q. 04. Which one of the following statements is incorrect regarding the reactions of pyridine ?

A It gives pyridine-N-oxide with H2O2/acetic acid

B It gives 2-aminopyridine with NaNH2/toluene
C It gives 3-nitropyridine with HNO3/H2SO4 in low yields
D It easily give Friedel craft acylated product with CH3COCl.

Q. 05. Which of the following has highest resonance energy ?

A Pyridine B Thiophene C Furan D Pyrrole

Q. 06. The reaction of DMF/POCl3 with pyrrole will yield:

Q. 07. The final product of bromination of furan in methanolic solution is:

....................................................................................................................................................................................
PTO Page 1
Q. 08. The correct IUPAC name of isoquinoline is

A Benzo[a]pyridine B Benzo[b]pyridine
C Benzo[c]pyridine D Benzo[d]pyridine

Q. 09. The major product of the following chemical transformation is:

Q. 10. The major product of the following chemical transformation is:

Q11. Natural products are usually regarded as;

(A) Primary metabolite (B) secondary metabolite
(C) tertiary metabolite (D) quaternary metabolite

Q12. The general formula of a sesterpenoid is:

(A) C20H32 (B) C25H40 (C) C30H48 (D) C40H64

Q13. Citral, mol. formula C10H16O, does not contain:

(A) CHO funct gp (B) two double bonds
(C) cyclohexane ring (D) three methyl gps.

Q14. The missing reagent in the following a-pinene reaction is

(A) HNO2 (B) HCl + HNO3 (C) NOCl (D) HNCO

Q15. When camphor is treated with benzaldehyde the corresponding benzylidene derivative is formed. This
shows that camphor has:
(A) bridged structure (B) an aldehyde group
(C) an alcohol group (D) an active methylene group

Q16. Which of the following statements is usually true regarding the ring fusion conformation of steroids:
(A) A & B rings are trans (B) B & C rings are cis
(C) C & D rings are trans (D) B &D rings are cis
....................................................................................................................................................................................
PTO Page 2
Q17. In the Salkowski color reaction gives red coloration for:
(A) Terpenoids (B) steroids (C) lipids (D) amino acids
Q18. Epi-cholesterol, which is obtained by chlorination followed by Grignard hydrolysis contains:
(A) 10- Me (B) 10- Me (C) 3- OH (D) 3- OH

Q19. Vitamin-D has a …………………………. Core:

(A) Terpenoid (B) steroid (C) alkaloid (D) isoprenoid
Q20. Estrone hormone undergoes which of the following tests:
(A) Herzig-Meyer (B) Hofmann degradation (C) Zeisel’s test (D) 2,4-DNP test

Q21. Which of the following releases the least energy when metabolised in the body:
(A) Proteins (A) fats (C) carbohydrates (d) vitamins

Q22. If an unknown natural product gives a ppt with phosphotungstic acid, it is most likely a:
(A) steroid (B) lipid (C) alkaloid (D) protein

Q23. Phosphatidyl choline contains a/an……………………….. group attached to the “O” of phosphorus:
(A) –H (B) –NH3+ (C) -CH2CH2-NH3+ (D) -CH2CH2-NMe3+

Q24. If you are administered a dose of adrenaline, it would usually lead to:
(A) sedation (B) hallucination (C) hypnotisation (D) increased perspiration

Q25. The most suitable reagent for the transformation in the synthesis of adrenaline would be:

(A) HNO3/H2SO4 + Cl2 (B) ClCH2COCH3 (C) ClCH2COCl (D) CH3COCl + Cl2

Q26. Nicotine requires a maximum of …………… moles of CH3I for the formation of its quaternary salt:
(A) two (B) three (C) four (D) five

Q27. Morphine contains the ……………………… nucleus in its structure:

(A) anthracene (B) phenanthrene (C) morphacene (D) fluorene

Q28. The Erlenmeyer synthesis of amino acids involves one of the following steps. Which of the following is
true for the azalactone product:

(A) it is a five-membered heterocycle with ester gp (B) it is a six-membered heterocycle with ester gp
(C) it is a five-membered heterocycle with lactam gp (D) it is a six-membered heterocycle with lactam gp

Q29. An amino acid solution acts as an acid because of the presence of …………………….. group:
(A) –COOH (B) –COO- (C) NH2 (D) NH3+
Q30. The Sanger method is used for……………………… while the Dansyl method is used for………………
of amino acids:
(A) N-terminal analysis, N-terminal analysis (B) C-terminal analysis, C-terminal analysis
(C) N-terminal analysis, C-terminal analysis (D) C-terminal analysis, N-terminal analysis
....................................................................................................................................................................................
END Page 3
 Birla Institute of Technology & Science, Pilani, Rajasthan - 333 031 SET Y
II Semester 2015-2016
nd

CHEM F342 ORGANIC CHEMISTRY IV

Comprehensive Examination (Closed Book)
Max. Marks: 30 Duration: 60 minutes Date: 11th May 2016
NOTE: There are THIRTY questions in all. Attempt all the questions. Indicate the most appropriate answer
by entering A, B, C or D in boxes provided in the front of each question. Do not overwrite. Each question
carries one mark. Part II may be collected after submitting Part I.

Q1. In the Salkowski color reaction gives red coloration for:

(A) Terpenoids (B) steroids (C) lipids (D) amino acids
Q2. Epi-cholesterol, which is obtained by chlorination followed by Grignard hydrolysis contains:
(A) 10- Me (B) 10- Me (C) 3- OH (D) 3- OH

Q3. Vitamin-D has a …………………………. Core:

(B) Terpenoid (B) steroid (C) alkaloid (D) isoprenoid
Q4. Estrone hormone undergoes which of the following tests:
(A) Herzig-Meyer (B) Hofmann degradation (C) Zeisel’s test (D) 2,4-DNP test

Q5. Which of the following releases the least energy when metabolised in the body:
(A) Proteins (A) fats (C) carbohydrates (d) vitamins

Q6. If an unknown natural product gives a ppt with phosphotungstic acid, it is most likely a:
(B) steroid (B) lipid (C) alkaloid (D) protein

Q7. Phosphatidyl choline contains a/an……………………….. group attached to the “O” of phosphorus:
(A) –H (B) –NH3+ (C) -CH2CH2-NH3+ (D) -CH2CH2-NMe3+

Q8. If you are administered a dose of adrenaline, it would usually lead to:
(A) sedation (B) hallucination (C) hypnotisation (D) increased perspiration

Q9. The most suitable reagent for the transformation in the synthesis of adrenaline would be:

(A) HNO3/H2SO4 + Cl2 (B) ClCH2COCH3 (C) ClCH2COCl (D) CH3COCl + Cl2

Q10. Nicotine requires a maximum of …………… moles of CH3I for the formation of its quaternary salt:
(A) two (B) three (C) four (D) five

Q11. The Erlenmeyer synthesis of amino acids involves one of the following steps. Which of the following is
true for the azalactone product:

(A) it is a five-membered heterocycle with ester gp (B) it is a six-membered heterocycle with ester gp
(C) it is a five-membered heterocycle with lactam gp (D) it is a six-membered heterocycle with lactam gp
....................................................................................................................................................................................
PTO Page 1
Q. 12. The correct structure of 6H-1,3-thiazine is

Q. 13. Which of the following compounds is least basic ?

Q. 14. Which one of the following products is obtained by the reaction between 2-phenyloxetane and HCN ?

Q15. Morphine contains the ……………………… nucleus in its structure:

(A) anthracene (B) phenanthrene (C) morphacene (D) fluorene

Q. 16. Which one of the following statements is incorrect regarding the reactions of pyridine ?

A It gives pyridine-N-oxide with H2O2/acetic acid

B It gives 2-aminopyridine with NaNH2/toluene
C It gives 3-nitropyridine with HNO3/H2SO4 in low yields
D It easily give Friedel craft acylated product with CH3COCl.

Q. 17. Which of the following has highest resonance energy ?

A Pyridine B Thiophene C Furan D Pyrrole

Q. 18. The reaction of DMF/POCl3 with pyrrole will yield:

Q. 19. The final product of bromination of furan in methanolic solution is:

Q. 20. The correct IUPAC name of isoquinoline is

A Benzo[a]pyridine B Benzo[b]pyridine
C Benzo[c]pyridine D Benzo[d]pyridine

Q21. Natural products are usually regarded as;

(A) Primary metabolite (B) secondary metabolite
(C) tertiary metabolite (D) quaternary metabolite
.............................................................................................................................................................................
PTO Page 2
Q22. The general formula of a sesterpenoid is:
(A) C20H32 (B) C25H40 (C) C30H48 (D) C40H64

Q23. Citral, mol. formula C10H16O, does not contain:

(A) CHO funct gp (B) two double bonds
(C) cyclohexane ring (D) three methyl gps.

Q. 24. The major product of the following chemical transformation is:

Q. 25. The major product of the following chemical transformation is:

Q26. The missing reagent in the following a-pinene reaction is

(A) HNO2 (B) HCl + HNO3 (C) NOCl (D) HNCO

Q27. When camphor is treated with benzaldehyde the corresponding benzylidene derivative is formed. This
shows that camphor has:
(A) bridged structure (B) an aldehyde group
(C) an alcohol group (D) an active methylene group

Q28. Which of the following statements is usually true regarding the ring fusion conformation of steroids:
(A) A & B rings are trans (B) B & C rings are cis
(C) C & D rings are trans (D) B &D rings are cis

Q29. An amino acid solution acts as an acid because of the presence of …………………….. group:
(B) –COOH (B) –COO- (C) NH2 (D) NH3+

Q30. The Sanger method is used for……………………… while the Dansyl method is used for………………
of amino acids:
(A) N-terminal analysis, N-terminal analysis (B) C-terminal analysis, C-terminal analysis
(C) N-terminal analysis, C-terminal analysis (D) C-terminal analysis, N-terminal analysis
....................................................................................................................................................................................
END Page 3