[CHEMPR0-SEM2] 2012/2013

CHAPTER 12 HYDROCARBON

2005/2006 1. (a) 2-bromobutane reacts with alcoholic sodium hydroxide solution to give major product, B and minor product, C. B is subsequently reacted with HBr to form D. i. Name the rule used for the formation of B and C. ii. Draw the structures of B, C and D. iii. Give the IUPAC name for B and D. [6M] (a) Arrange the following compounds in order of increasing boiling point. Explain. 2-methylpentane hexane 2,3-dimethylbutane 2,2-dimethylpentane [5M] (b) Give structural formulae for products A and B in the following reactions: i.

2.

i. O3 ii. Zn, H 2O H2O2 (CH3)2C=CHCH3 + HBr

ii. 2006/2007 3.

B [2M]

(a) Compound K, C5H10 reacts with bromine in the presence of ultraviolet light to give only L, C5H9Br. Compound K does not react with acidified solution of potassium manganite (VII). Upon treatment with potassium t-butoxide, L gives only one product, M, C5H8. M decolourised bromine water and ozonolysis of M gives N, C5H8O2. Deduce the structures of compounds K through N. Write an equation for the reaction of M with bromine water. [8M]

(b) Alcohol can be used as the starting material in synthesizing various organic compounds as shown in the reaction scheme below. Propose the structures for P and Q.
H HOCH2 C H CH3 C H CH3 conc. H2SO4 P major HCl Q

Give the mechanism for the formation of P. 2007/2008

[7M]

4. Compound X, C7H14 is optically active. On catalytic reduction of X over palladium, one mole equivalent of hydrogen was absorbed yielding compound Y, C7H16. Reaction of X with Page 1

[CHEMPR0-SEM2] 2012/2013 hot acidified solution of potassium permanganate gives ethanoic acid and compound Z, C5H10O2 which is an optically active carboxylic acid. Draw the structure for X, Y and Z. Explain your answer. Give the IUPAC name of X. Propose a mechanism for the reaction of X with HCl that leads to the formation of the major product. Suggest a chemical test to distinguish compound X from Y. State the observation and write the chemical equations. [15M] 2008/2009 5. Compound A has molecular formula of C7H14. A reacts with bromine in dichloromethane to form 1,2-dibromo-3,4-dimethylpentane. Treatment of A with HCl gives B and C. a) Draw the structural formula of A, B and C. [3M] b) Draw the structures of the carbocation intermediates in the formation of B and C. Indicate the more stable carbocation and give your reason. [4M] c) Name the type of reaction for the formation of B and C. [1M] d) Predict whether A can exist as a stereoisomer. Explain your answer. [2M] 2009/2010 6. 2,2,4-trimethylpentane, Q, is used as an antiknock agent in the combustion technology. Monobromination of Q gives R as a major product. R undergoes dehydrohalogenation to form S and T. Oxidative cleavage of S gives two products, U, a ketone and V, a carboxylic acid. Write chemical equations for the complete and incomplete combustions of Q, monobromination of Q and oxidation of S. Explain the formation of R in terms of radical stability. Suggest the structures of S, T, U and V. By using a two-step reaction, show how U can be prepared from an alkene of your choice. [15M] 2010/2011 7. (a) Dehydration of alcohol G gives compounds H and J. Draw the structures of H and J. determine the major product and show the mechanism for its formation. CH2CH2OH

G (b) Compound L, C10H20 reacts with hot acidified solution of potassium permanganate to form hexanoic acid and isobutyric acid, CH3CH(CH3)COOH. Draw the structure of L and give its IUPAC name. [5M]

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[CHEMPR0-SEM2] 2012/2013 2011/2012 8. (a) Based on the reaction scheme below :

CH3CH2CH2CH3

B
(major product)

C
OH CH3CHCH2CH3

i.

Give reagents A and C, and the structure of B. Show initiation, propagation and termination steps in the mechanism for the formation of B. [8M]

(b) Acid-catalysed dehydration of 1-pentanol gives a mixture of alkenes. i. Draw the structures of all the products formed, and label the major product. ii. State the rule used to determine the major product. iii. Write the chemical equations when the minor product reacts with chlorine gas; acidified water; and bromine water. [7M] 9. 2-Methylpentane reacts with Br2 in the presence of light to yield L, a monobromination product. Dehydrohalogenation of compound L forms M and N as the respective major and minor products. Oxidative cleavage on M gives ketone P and carboxylic acid Q; whereas similar reaction on N forms ketone R and CO2. Treatment of M with acidified water yields S.Write the chemical equations for complete combustion of 2methylpentane; dehydrohalogenation of L; and oxidative cleavage of M. Suggest the structures of L, M, N, P, Q, R and S. Write the mechanism for the formation of S. [14M]

CHAPTER 13 BENZENE AND ITS DERIVATIVES 2005/2006 1. Compound Q is obtained when benzene reacted with CH3Cl/AlCl3. Nitration of Q gives compound R and S. Reaction of Q with chlorine in the presence of uv light gives compound T, C7H7Cl. Compound U is formed when T is treated with KCN. Hydrolysis and reduction of U give carboxylic acid, V and amine, W respectively. Give the structure of Q, R, S, T, U, V and W. [7M] 2007/2008 2. Benzaldehyde is an aromatic aldehyde which can be found in bitter almonds. Show how benzaldehyde can be synthesized from benzene. [8M]

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[CHEMPR0-SEM2] 2012/2013 3. The structure of 4-hydroxyazobenzene is as shown.

Suggest how the above compound can be synthesized using benzene and phenol. [7M] 2009/2010 4. Alkylation of benzene using 2-chloropropane in the presence of AlCl3 gives compound W. Bromination of W in the presence of light yields X, which gives 2-phenylpropene when treated with reagent Y. Treatment of 2-phenylpropene with reagent Z gives 1bromo-2-phenylpropane. Treatment of 1-bromo-2-phenylpropane with aqueous sodium hydroxide gives compound AA. Oxidation of AA with PCC forms BB. Benzoic acid is obtained when W reacts with reagent CC. Identify the reagent Y, Z and CC and give the structures of W, X, AA and BB. Give the mechanism for the formation of W. Draw the structure of the product formed when X reacts with 1-propanol. Name the type of reaction and suggest the mechanism for the formation of the product [15M] 2010/2011 5. Starting from benzene, show how you would prepare 3-nitrobenzoic acid using suitable reagents and conditions. Give another method to prepare the same final product from chlorobenzene. [10M] 2011/2012 6. Indicate the reagents needed for the following conversions : a) Benzene to acetophenone

[1M]

7. Compound T is formed from the reaction of benzene with chloroethane in the presence of AlCl3. Chlorination of T in light gives monochlorinated compounds U (major product) and V. Treatment of T in acidified solution of KMnO4 produces W. Hydrolysis of U forms X ; whereas reaction of U with nucleophile Z produces Y, C6H5CH(OCH2CH3)CH3. Reagent AA transforms X to acetophenone while reagent BB converts the acetophenone to carboxylic acid. Draw the structure of compounds T, U, V , W and X and state the reagents AA and BB. Name the reaction for the formation of T and write the mechanism. State whether the hydrolysis of U occurs via SN1 or SN2 mechanism and show the mechanism chosen. Give the nucleophile Z. Compounds Y is optically active. Draw a three-dimensional structural formula for an enantiomeric pair of Y. [20M]

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