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Name ____________________________________________________________

Student Number ___________________________________________________

CHM B44Y TEST 3

12 February 2003

TIME ALLOWED: 100 MINUTES

No models, calculators or other electronic equipment allowed.

Tests and exams must be written in non-erasable ink. If you write in pencil or erasable ink, your right to have your test re-marked may be forfeit. Please do not use red ink. Answers all of the questions in the spaces provided. The number of marks available are indicated in parantheses by the questioni: total marks for test = 100. For convenience the spectroscopy questions are at the end of the test. Also given at the end of the very end of the paper is a table of characteristic IR, 1H NMR and 13C � NMR frequencies and chemical shifts.

Question Marks Total Marks Available

1. Reactions 20

2. Reagents 10

3. Synthesis 18

4. Mechanisms 12

5-8. Spectroscopy 40

TOTAL MARK 100

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1. (20 Marks) Give the major products of the following reactions. (There is a product for every question.)

CH3O

NH2

Cl

Cl

CH3O CH2CH3

CH2CH3CH3CH2

CH3CH2CH2

CH3CH2CH2

O

C

CN

O

CH3

COOH

O

OCCH3 O C

O

CH3

OC ClCH3CH2

(j)(j)

(i)(i)

(h)

(h)

(g)

(f)

(g)

(f)

(e)(e)

(d)

(d)

(c)(c)

(b)

(b)

(a)

(a)

NaCN

+ excess PhNH2

NaOCCH3SOCl2

HNO3, H2SO4

+ CH3CH2CCl

1. AlCl32. Zn(Hg), HCl

AlCl3+ CH3CH2CH2Cl

KMnO 4, H+, heat

excessCl2, FeCl3

1. NaNO2, HCl, 0o C2. CuCl

HNO3, H2SO4

3

2. (10 marks). Provide reagents that achieve the following transformations. Note more than one step may be required.

NO2 OH

C OCOOH

OHBr

BrBr

O

CO

NH2CO

OCH2CH3(c)

(b)

(a)

4

3. (18 marks) In the space provided, provide a synthetic route for converting benzene into the indicated compounds. You can use any other reagents.

CH2CH2CH2CH2CH3

NO2

(a)

Cl

Cl(b)

NH

CO

CO

NH

(c)

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4. (12 marks). Give mechanisms for the following reactions. Indicte the flow of electrons by using curved arrows, and write the structures of the intermediate structures.

(a) The mechanism for the acid hydrolysis of amides.

OCCH3CH2 NH2

OCCH3CH2 OH+ + NH4

+H++ H2O

(b) The mechanism for the reaction known as protodesilylation.

SiMe3 H+ HOSiMe3

H2SO4,H2O

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5. (6 marks). How many peaks would each of the following molecules have in the 1H NMR spectra and in their 13C NMR spectra?

C CH3C

H3C

C(CH3)3

CO

CH3

H3C

H3C

CH2OCH3

No. of 1H NMR peaks ________No. of 13C NMR peaks ________

� Cl-+

6. (6 marks) Draw a splitting diagram for the Hb proton if Jbc = 8 and Jba = 4.

H

Cl CHCl2

Hc

ba 7. (4 marks). Compound A (C10H18) has a single sharp peak at 1.2 ppm in its 1H NMR

spectrum. What is its structure? 8. (24 marks). The IR, 1H NMR and 13C NMR spectra for compounds B, C, D and E are

shown on the next pages. Determine the structure of these compounds and draw them below.

B (C8H8O2) C (C5H10O2) D (C7H14O) E (C9H10)

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CHMB44 Test February 12, 2003 - Answers 1. (20 Marks) Give the major of products of the following reactions. (There is a product

for every question.)

CH3O

NH2

Cl

Cl

CH3O CH2CH3

CH2CH3CH3CH2

CH3CH2CH2

CH3CH2CH2

O

C

CN

O

CH3

COOH

O

OCCH3 O C

O

CH3

OC ClCH3CH2

CH3O NO2 CH3O

NO2

Cl

Cl

Cl

CH3CH2CH2 CH2CH2CH3

CH2CH3

Cl

Cl

CH3O

COOHHOOC

CH3CH2CH2 CHCH3

CH3

CCN

OCH3

NO2

CO

O CO

CH3

OCCH3 O C

O

CH3NHPh

OC CNCH3CH2

-++PhNH3

+ ortho

+ ortho

+ HNO3, H2SO4

1. NaNO2, HCl, 0o C2. CuCl

Cl2, FeCl3excess

KMnO 4, H+, heat

+ CH3CH2CH2ClAlCl3

1. AlCl32. Zn(Hg), HCl

+ CH3CH2CCl

HNO3, H2SO4

SOCl2 NaOCCH3

+ excess PhNH2

NaCN

(a)

(a)

(b)

(b)

(c)(c)

(d)

(d)

(e) (e)

(f)

(g)

(f)

(g)

(h)

(h)

(i)(i)

(j)(j)

2

2. (10 marks). Provide reagents that achieve the following transformations. Note more than one step may be required.

NO2 OH

C OCOOH

OHBr

BrBr

O

CO

NH2CO

OCH2CH3

OH

1. H+ or OH-, H2O2. CH3CH2OH, H+

orSOCl2, then CH3CH2OH

1. SOCl22. 1. CH3Cl, AlCl3

2. KMnO 4, H+

Excess Br2, H2O

1. H2/Pd or Fe/HCl2. NaNO2, H, 0oC3. Heat

(a)

(b)

(c)

3. (18 marks) In the space provided, provide a synthetic route for converting benzene

into the indicated compounds. You can use any other reagents.

CH2CH2CH2CH2CH3

NO2O

CCH2CH2CH2CH3

OCCH2CH2CH2CH3

NO2

O

Zn(Hg),HCl or H2NNH2, NaOH

HNO3H2SO4

ClCCH2CH2CH2CH3, AlCl3

(a)

3

Cl

Cl

NO2 NO2

Cl

NH2

Cl

N2+

Cl

CuCl

NaNO2, HClH2, PdCl2,FeCl3

(b)

NaNO2H2SO4

NH

CO

CO

NH

NO2 NH2

ClCO

CO

Cl

(c)

H2/Pd

NaNO2, H2SO4

4. (12 marks). Give mechanisms for the following reactions. Indicte the flow of electrons

by using curved arrows, and write the structures of the intermediate structures. (a) The mechanism for the acid hydrolysis of amides.

OCCH3CH2 NH2

OCCH3CH2 OH

OHCCH3CH2 NH2 CH3CH2 C

OHNH2

OH2

CH3CH2 COH

NH2OH

CH3CH2 C

OH

NH3OH

OHCCH3CH2 OH

(a)

��+

+ NH3

��

+

+�� OH2

+H+

+ NH4+

(b) The mechanism for the reaction known as protodesilylation.

SiMe3 SiMe3H

H

Me3SiŠOH

-H+

+Me3SiŠOH2

�� OH2

+ Me3Si++H+

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5. (6 marks). How many peaks would each of the following molecules have in the 1H NMR spectra and in their 13C NMR spectra?

C CH3C

H3C

C(CH3)3

CO

CH3

H3C

H3C

CH2OCH3

1

1

7

5

8

4

+� Cl-

No. of 1H NMR peaks ________No. of 13C NMR peaks ________ 6. (6 marks) Draw a splitting diagram for the Hb proton if Jbc = 8 and Jba = 4.

H

Cl CHCl2

Halso 4 Hz 4 peaks of equal intensity,

each separated by 4 Hz4 Hz4 Hz

8 Hz

a b

c

7. (4 marks). A compound A C10H18 has a single sharp peak at 1.2 ppm in its 1H NMR

spectrum. What is its structure? 8. (24 marks). The IR, 1H NMR and 13C NMR spectra for compounds B, C, D and E are

shown on the next pages. Determine the structure of these compounds and draw them below.

C C C(CH3)3(CH3)3CA B (C8H8O2) C (C5H10O2)

CH3O C

O

HCH3CH2 C

O

OCH2CH3 D (C7H14O) E (C9H10)

OCCH3 CH2CH2CH2CH2CH3 C

CH3

C HH