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AS/APR 2010/CHM522

UNIVERSITI TEKNOLOGI MARA FINAL EXAMINATION

COURSE COURSE CODE EXAMINATION TIME

: : : :

ORGANIC CHEMISTRY II CHM522 APRIL 2010 3 HOURS

INSTRUCTIONS TO CANDIDATES 1. 2. 3. 4. This question paper consists of ten (10) questions. Answer ALL questions in the Answer Booklet. Start each answer on a new page. Do not bring any material into the examination room unless permission is given by the invigilator. Please check to make sure that this examination pack consists of: i) ii) the Question Paper an Answer Booklet - provided by the Faculty

DO NOT TURN THIS PAGE UNTIL YOU ARE TOLD TO DO SO

This examination paper consists of 9 printed pages
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QUESTION 1 Reactions (I), (II) and (III) concern Aldol condensation and reaction (IV) is Cannizzaro reaction. Answer the questions below pertaining these reactions. OH'^ W 2 | f ^ T O * 0 " ~" Product (before dehydration) O OH(II) Product *" (after dehydration)

(III)

OH-

(IV)

? + ?

a)

For reaction (I): i) Draw the structure of the product formed before and after dehydration, ii) Draw the structure of the enol form of the starting ketone. (4 marks) For reaction (II), draw the structure of the starting dicarbonyl compound needed to produce the cyclic product above. (2 marks) For reaction (III): i) Draw the structure of the starting carbonyl compounds that undergo the crossed Aldol condensation reaction to give the above product, ii) Draw the structure of the enolate ion that is generated during the course of the reaction in its two resonance forms. (5 marks) For reaction (IV), draw the structure of the products obtained. (2 marks)

b)

c)

d)

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QUESTION 2 Reactions (I) and (II) below concern Robinson Annulation reaction which begins with Michael addition reaction and ends with intramolecular aldol condensation.

(I)

Ketone A

Enone B

OHX(CH3)3 Robinson product

(II)

OH-

Michael addition product

Robinson product

a)

For reaction (I), draw the structure of the starting ketone A and the enone B that undergo the Robinson Annulation reaction to give the Robinson product. (2 marks) For reaction (II), write the step-wise mechanism for the Robinson Annulation reaction. Label the Michael addition product and the Robinson product. (19 marks)

b)

QUESTION 3 This question concerns Claisen condensation reactions. O \\ . 1.CH,0 (I) (CH3)2CH-C(CH3)2CH2-C-OCH3 2. H 3 0
+

1. Base

(ID

2. H 3 0 + (Dieckmann) O O

(III)

1. CH30? + ? 2. H 3 0 +

a)

Draw the structure of the product of reaction (I), the product of reaction (II) and the starting esters for reaction (III). (6 marks)

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b)

For reaction (II), draw the structure of the enolate ion generated during the reaction and then draw the two curved arrows to illustrate the cyclization process. (2 marks) For reaction (III), write the mechanism starting with the appropriate enolate ion right until the final product is obtained. (10 marks)

c)

QUESTION 4 The equations below represent two known organic syntheses which begin with different esters but follow similar sequence of reactions. Synthesis (I) O o || II CH3CH20-C-CH2-C-OCH2CH3
1

- NaOCH2CH3 2. CH3CH(CH3)CH2CH2Br 3. H30+, heat

Synthesis (II) 1. NaOCH2CH3; R-CI 2. NaOCH 2 CH,; R'-CI - + 3. H 3 0 , heat

Q CH II 3 CH,-C-CH-CHXH.,-CH-CH-CH, -CH-CH2CH2-CH-CF CH2-C(CH3)3 CH

a)

Name synthesis (I) and synthesis (II) (2 marks)

b)

Complete the equations above by drawing the structures of the organic product of synthesis (I) and the starting ester of synthesis (II). (3 marks) Write the structural formula of reagent R-CI and reagent R'-CI, that are required to synthesize the product in synthesis (II). (2 marks) Write the step-wise mechanism for synthesis (I). (14 marks)

c)

d)

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QUESTION 5 All reactions below involve carbocation rearrangement by ring expansion. Only reactions (II) and (III) undergo a second type of rearrangement after ring expansion. Only product V of reaction (I) and product X of reaction (II) are formed before ring expansion. Some other possible products might form other than the ones shown.
.. (I) CH2CH3 CHBr-CH, CH3CH2OH Heat

{J-

or \ o<
/\.CH2CH3 ^~^^CH, Product U *CH3 Product W Product X Product Y

OCH2CH3 CH(CH3)CH2CH3

Product V

(II)

CH(OH)-CH3

HI

(III)

Q=CH, CH,

HBr

(IV)

OH

H 2 S0 4 Product Z

a)

For reaction (I): i) State the type(s) of reaction(s) occurring. ii) Write separate mechanisms to account for the formation of the product U and product V. State the type of each carbocation intermediate involved whether it is a primary, secondary or tertiary. (18 marks) For reaction (II): State the type of reaction occurring. i) Draw the structure of the carbocation intermediate formed immediately after ring ii) expansion and after the second rearrangement respectively that leads to the formation of product W. iii) The second product (product X) is formed before ring expansion and involves a different type of carbocation rearrangement. Draw the structure of product X. (5 marks) For reaction (III): i) State the type of reaction occurring and state the type of the second rearrangement after ring expansion, ii) Draw the structure of product Y. (4 marks) For reaction (IV), state the type of reaction occurring and draw the structure of product (2 marks)

b)

c)

d)

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QUESTION 6 " O - O - C O - C H , X \ / \

? +

? product

+ CH3COOH

starting materials

Unstable intermediate The unstable intermediate shown above is formed in a Baeyer-Villiger reaction which involves rearrangement. a) Draw the structures of the starting materials and the principal product of the reaction. (3 marks) Supply curved arrows on the unstable intermediate above to show the rearrangement occuring. (2 marks)

b)

QUESTION 7 a) Pyridine undergoes substitution reaction with nitric acid, HNO3 with difficulty. i) Draw the structure of the principal organic product formed and name the product, ii) Explain why pyridine is very unreactive. (5 marks) Pyrrole undergoes electrophilic substitution reaction with Cl2 with ease. i) Write the formula of the electrophile involved in this reaction. ii) Draw the structure of the principal organic product formed and name the product. iii) Explain why pyrrole is very reactive. (6 marks) c) Furan undergoes Friedel-Crafts acylation with CH3COCI/SnCI4. Write the mechanism for this substitution reaction starting with the addition of the electrophile. Include all three resonance contributors of the carbocation intermediate. (7 marks) Isoquinoline and indole are fused-ring heterocyclic compounds. i) Draw the orbital diagram, showing (label some) all p orbitals, % electrons, other lone electron pair (if any) and its orbital(s) for isoquinoline. ii) Draw the structure of the product obtained from sulfonation of indole. Name the product, iii) Draw one possible resonance contributor of the carbocation intermediate formed in the bromination reaction of isoquinoline. (10 marks)

b)

d)

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QUESTION 8 a) Given below are two reactions of D-sugar P where reaction I yields product Q and reaction II yields product R. D-sugar P exists in furanose and pyranose forms. CH2CH3OH, H+

CH 2 OH 0

OCH2CH3 CH2OH

Reaction I D-sugar P CH3COCI, pyridine Reaction II i) ii) iii) iv)

H OH Product Q Product R

Draw in Haworth projection, the furanose form of product R. Draw the chair form of D-sugar P. What class of monosaccharide does D-sugar P belong to? Reaction I actually produces two anomeric products but only product Q is given. What are these two anomeric products called and what type of anomer is product P? (9 marks)

b)

Consider the following chain-lengthening synthesis of Aldose T to form aldose U and aldose V. CHO 1. NaCN, HCI H-OH 2. H20, H+ HO-H Aldose T Aldose V 3. NaBhL -OH HCH2OH Aldose U i) ii) iii) iv) What is the specific name of the above synthesis? Draw the structure of aldose T and aldose V. Aldose U and aldose V are epimers. What type of epimers? Draw the structure of the intermediate products formed after the addition of the first reagent, NaCN, HCI. (7 marks)

c)

On Ruff degradation, D-glucose is converted to D-arabinose. D-arabinose converts to an optically active alditol K upon reduction with NaBH4. Show that Ruff degradation of D-glucose produces D-arabinose and draw the linear form of alditol K in Fischer projection. (12 marks)

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QUESTION 9 Consider the Grignard reactions below.

(I)

,MgBr

.MgBr 2. H,0 + H,0 +

2. H 3 0 +

(II)

MgCI

(III)

hAlH
(IV) ? + 0 ?

H30+ (CH3)2CHCH(CH3)CH2CH2OH H30+ OHy \\ // H,0 +

(V)
H

^ / \ ^ M g C I

a)

Draw the structure of the starting material(s) / product(s) for each reaction above. (10 marks) For reaction (II), give one other possible combination of a different carbonyl compound and a different Grignard reagent to obtain the same alcohol product of reaction (II). (2 marks) For reaction (IV), i) give the IUPAC name of the Grignard reagent used. ii) write an equation for the preparation of this Grignard reagent. (4 marks)

b)

c)

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QUESTION 10 2,5-dimethylheptane can be prepared via two routes, I and II. ROUTE I ether + Cul organolithium

alkyl halide F

+ 2 Li

(CH3),CuLi

alkyl halide G

ROUTE II (CH3)2CHCH,-CI +

Gilman reagent 2,5-dimethylheptane

a)

Draw the structure of alkyl halide F, alkyl halide G, the organolithium and the Gilman reagent to complete the scheme above. (5 marks) Name the organolithium involved via route I and name the Gilman reagent involved via route II. (3 marks) Write the formula of the two side products of the reaction via route II and name this reaction. (3 marks)

b)

c)

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