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SINHA IIT CHEMISTRY 1

TEST GOC & POC


1 : Write the pKa below the phenol to which it corresponds. Briefly explain your reasoning. pKa choices: 7.15,
10.00, 10.46

2: a. Rank the following compounds in order of increasing acidity.

E IT A
Order: (least acidic) < < (most acidic)
b. Provide the structure of a dicarbonyl compound which is clearly more acidic than any of the compounds shown
H I H

Y
above.
N

TR
3 : a. Rank the following phenols in order of acidity.
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M

b. Briefly explain your ranking.

4 : Consider the isomeric compounds biphenyl and acenaphthene:


C

a. Identify the more stable isomer: biphenyl acenaphthene

5. Identify the most stable alkene isomer.

A B C.

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SINHA IIT CHEMISTRY 2

6. Circle the worst nucleophile: HO- CH3CO2- CH3O-

7. Circle the worst leaving group: F- I- CH3-


+
8 Circle the least stable carbocation: CH3 H2COH+ H2CNH2+

9..Circle the compound with the lowest dielectric constant: H2O CH3OH CF3OH

10: Circle the molecule that is less stable and very briefly explain your answer.

11: Circle the most nucleophilic ion or molecule in each set.

b. NH3 H2O CH3OCH3


c. CH3CH2CH2O- CH3CF2CH2O- CF3CH2CH2O-

12-Compound W, C3H8O, reacts with hot concentrated phosphoric acid to give X, C3H6, which rapidly decolourises a
E IT A
solution of bromine in tetrachloromethane. On treatment with ethanoyl chloride, W gives Y, C5H10O2. Oxidation of W
with potassium dichromate in dilute sulphuric acid gives Z, C3H6O, which gives an orange precipitate with 2,4-
H I H
dinitrophenylhydrazine but does not react with an ammoniacal solution of silver nitrate.

Y
Deduce the structures of W, X, Y and Z, explaining carefully what each piece of evidence tells you.
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13-An oily liquid A is insoluble in water, but on heating with aqueous sodium hydroxide solution for half an hour it
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dissolves. From the reaction mixture a liquid B can be distilled, which gives a yellow precipitate with iodine and
sodium hydroxide solution. On careful oxidation B gives an aldehyde, C, which also gives a yellow precipitate with
IS
iodine and sodium hydroxide solution. If sulphuric acid is added to the solution obtained from heating A with sodium
hydroxide solution, a white precipitate D is obtained. D liberates carbon dioxide from sodium hydrogen carbonate
solution, one mole of D reacting with sodium hydrogen carbonate to give one mole of carbon dioxide. Heating D with
M

soda-lime* converts it to benzene.


Find the structures of A, B, C and D, giving your reasoning.

• Soda-lime is calcium oxide that has been slaked with sodium hydroxide solution. Carboxylic acids, on
heating with soda-lime, are decarboxylated, that is the -COOH group is replaced by -H.

14-Compound A, C4H8O2, gives an orange precipitate with 2,4-dinitrophenylhydrazine reagent, and a silver mirror with
ammoniacal silver nitrate. A is converted to B, C4H6O, on treatment with acid. B may exist as a cis- or trans- isomer; it
C

reacts with hydrogen chloride to give C, C4H7OCl, and with chlorine to give D, C4H6OC12.
Reduction of C gives E, C4H9OCl, which is hydrolysed by dilute alkali to F, C4H10O2. Both A and F give a positive
iodoform (CHI3) test, whereas E does not.
Identify compounds A to F.

15-An alcohol has the molecular formula C4H7OH. Oxidation of this alcohol gives a ketone. Ozonolysis of this alcohol
gives methanal as one of the products.Giving your reasoning in full, deduce the structural formula for this alcohol and
predict whether it will be optically active.

Ozonolysis is a technique for finding the position of C=C double bonds in a molecule. The compound is reacted with
ozone-enriched oxygen in a suitable inert solvent, and the product is hydrolysed with ethanoic acid in the presence of
zinc. This produces a mixture of carbonyl compounds, which may be separated and identified, for example by means of
their 2,4DNP derivatives .

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SINHA IIT CHEMISTRY 3

16 Iodoethane CH3CH2I reacts with aqueous sodium hydroxide solution to give A, with ammonia to give B, and with
potassium cyanide in ethanolic solution to give C, C3H5N. C reacts with lithium aluminium hydride in dry ether
solution to give D. C with aqueous sodium hydroxide solution followed by dilute hydrochloric acid gives E, C3H6O2,
which with phosphorus(V) chloride gives F.
Identify compounds A to F, giving your reasons and equations where appropriate.

17.A, C3H7Cl, reacts with aqueous sodium hydroxide solution to give C, C3H8O. C reacts with phosphorus
pentachloride to give steamy fumes, and can be oxidised with acidified potassium dichromate solution to give D,
C3H6O, and then E, C3H6O2. D reacts with both 2,4-dinitrophenylhydrazine and ammoniacal silver nitrate. E reacts
with phosphorus pentachloride and with sodium hydrogen carbonate solution, in the latter case giving carbon dioxide.
A will react with benzene in the presence of anhydrous aluminium chloride to give B, C9H12. The structure of this
compound is not what might have been expected from A. B can be made from benzene and F as the expected product,
however, F being an isomer of A. Sodium hydroxide solution converts F to G, an isomer of C. G can be oxidised with
acidified potassium dichromate solution to H, an isomer of D, but no further. H gives a positive result with the 2,4-
DNP test but not the ammoniacal silver nitrate test; it also gives a positive result in the iodoform reaction.
On heating with alkaline potassium manganate(VII) solution B gives an aqueous solution of I, which on treatment with
E IT A
dilute sulphuric acid gives a white precipitate J.
(a) Identify all of the substances A – J, and explain each of the observations as fully as you can with supporting
H I H
equations.

Y
(b) Suggest why A and F give the same product with benzene.
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18-A, C2H4, reacts with hydrogen bromide in the gas phase to give B, C2H5Br. This reacts with aqueous sodium
hydroxide solution to give C, C2H6O, which can be oxidised by acidified potassium dichromate solution to give
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successively D, C2H4O, and E, C2H4O2. D reacts with both 2,4-dinitrophenylhydrazine and ammoniacal silver nitrate.
With magnesium in dry ether B gives F, C2H5MgBr; this reagent will react with D to give G, C4H10O. Oxidation of this
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compound with acidified potassium dichromate solution gives H, C4H8O. This will also react with F, giving I, C6H14O.
I is not oxidised by acidified potassium dichromate solution.
If A is reacted with bromine in the presence of sodium chloride, two compounds are obtained; J, C2H4Br2, and K,
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C2H4BrCl. No C2H4Cl2 is formed.


(a) Identify each of the compounds A – K, and explain all the observations as fully as you can.
(b) Why is no C2H4Cl2 formed in the reaction given in the last paragraph?

19-Compound A, C4H8O, reacts with a solution of iodine in sodium hydroxide to give B, C3H5O2Na, and CHI3. A
gives a precipitate with 2,4-dinitrophenylhydrazine but no reaction with ammoniacal silver nitrate.
A can be reduced with lithium aluminium hydride in dry ether to give C, C4H10O, which is chiral. With sodium
chloride in 50% sulphuric acid C gives D, C4H9Cl. With magnesium in dry ether D gives G, C4H9MgCl; G will react
C

with solid carbon dioxide to give an intermediate which when treated with dilute hydrochloric acid gives H, C5H10O2.
If D is heated with potassium hydroxide dissolved in ethanol, three compounds are formed; E is the major product and
has two stereoisomers, and F is the minor product. Both varieties of E, and F, are C4H8.
C reacts with H in the presence of sulphuric acid catalyst to give I, C9H18O2.

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