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CHEM*2700 ORGANIC CHEMISTRY I Winter Semester, 2007

Department of Chemistry University of Guelph

Second Mid-term Examination March 24, 2007 (Saturday)

Duration: 1 hour and 30 minutes Total Marks = 100

(The exam consists of 8 questions plus a bonus question on 11 pages.) Instructor: William Tam

Q. 1 (10 marks) Q. 2 (22 marks) Q. 3 (8 marks) Q. 4 (15 marks)

Q. 5 (8 marks) Q. 6 (11 marks) Q. 7 (10 marks) Q. 8 (16 marks) TOTAL (100 marks) Bonus Marks (max. 6 bonus marks) 100 6

Answer all questions directly on the pages provided. Use the back of the pages for rough work. Anything on the back of the pages will not be graded. Please write in ink and only papers written in ink may be submitted for re-grading.

1.

In each of the following question, select the correct compound.

(10 marks)

O (a) A1 OCH3 O O A2 A3 A1 A3 O (b) B1 CH3 B2 OMe OMe B3 B4 O B3 B2 A4 OCH3 Cl

Reacts fastest in aromatic electrophilc substitutions: Reacts slowest in aromatic electrophilc substitutions:

Reacts fastest in electrophilic additions (e.g. with Br2 in CCl4): Reacts slowest in electrophilic additions (e.g. with Br2 in CCl4):

COOMe (c) C1 C2

Cl

CH3

Bu

C3

C4 C4 C1

Produces the highest percentage of the para isomer in nitration: Produces the highest percentage of the meta isomer in nitration:

Br (d) D1 D2

Br

Br

Br D4

D3 D4 D1 D2 D1

Reacts fasterest in SN1 reactions: Reacts slowest in SN1 reactions: Reacts fasterest in SN2 reactions: Reacts slowest in SN2 reactions:

2.

Give the structure of the major organic product in each of the following reaction. Clearly indicate stereochemistry where appropriate.
Cl O

(a)

CF3

O OH

(1 equiv.)

CF3 (3 marks)

Br (b) Ph Ph Br2 (1 equiv.) Ph Br (3 marks) Ph

(c)

CH2I2, Zn/Cu

(3 marks) O (d) O AlCl3

O Cl

O O O (3 marks)

(e)

OH

NaH

(3 marks) OH (f) Ph CN HOBr Ph Br CN (3 marks)

(g)

Hg(OAc)2
OH

O HgOAc (3 marks)

NaBH4 NaOH

(1 mark)
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3.

Provide suitable reagent(s) (a)(d) for each of the following transformations. (a) Ph Ph (b) Br Ph Br CH3 (b) = HBr (2 equiv.) Cl Cl (a) = CHCl3, tBuOK

(8 marks)

Ph

(c)

SO3H (c) = SO3, conc. H2SO4

CH3

(d)

Br

(d) =

Br2, h

4. Provide a detailed mechanism for each of the following conversions. Show all intermediates (including all the resonance structures where appropriate) and use curved arrows to show the direction of electron flow. Br2 OH N Answer:
+

(a)

Br

(5 marks)

Br

Br OH

Br
+

OH

N O Br

H O

Br

(b) Answer:
H Cl:

HCl, AlCl3

(5 marks)

+ AlCl3

+ H

Cl

AlCl3

H+ +

AlCl4

H+ H

r r

Cl

AlCl3

HCl

AlCl3

(c)

ROOR Ph Answer: RO OR
2 RO

heat

H H C C H Ph

(5 marks)
n

(Polystyrene)

RO

H2C CHPh

RO CH2CHPh H H H H RO C C C C H Ph H Ph H2C CHPh H H C C H Ph H H C C H Ph

RO CH2CHPh

H2C CHPh

(Polystyrene) H H H H RO C C C C H Ph H Ph H H H H C C C C H Ph H Ph

(Polystyrene)
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5.

Provide simple chemical tests to distinguish the following pairs of compounds. In each case, indicate: (i) what reagent(s) you need to use in the chemical test; (ii) the observation of the chemical test on each compound; and (iii) write all appropriate chemical equations that involved in the chemical test. OH (a) vs. OH

(8 marks)

(i) Reagent(s): NaOH (aq)

(ii) Observations:
Phenol: miscible/soluble in aq NaOH, one layer only Cyclohexanol: immiscible/insoluble in aq. NaOH, two layers

(iii) Chemical equations: OH NaOH OH NaOH No Reaction O Na + H2O

(b)

vs. (i) Reagent(s):

Ph

Ph (ii) Observations:
Alkyne: Decolorize Br2/CCl4 (the reddish-brown color of the Br2/CCl4 solution will turn to colorless) Benzene: The reddish-brown color of the Br2/CCl4 solution remains unchanged

Br2, CCl4

(iii) Chemical equations:

Br2 CCl4

No Reaction Br Br Ph Br Br

Ph

Ph

Br2 CCl4

Ph

6. In each of the following, draw the structure of the unknown compound. e.g. An unsymmetrical ether with molecular formula C4H10O. Answer:
O

(11 marks)

(a) Compound A (C4H8) gives a meso compound B upon treatment with Br2/CH2Cl2.
Compound A: Wedge-and-dash structure of Compound B:
Br

(4 marks)

Fisher Projection of Compound B: CH3

Br
Br

H or
Br Br Br

Br Br CH3

H )

(same as:

(b) An aromatic alkyne C (C8H6) produced an aldehyde D by hydroboration-oxidation. catalyzed hydration of C gave a ketone E.

Mercury-

(4.5 marks)

Compound C: H

Compound D:

Compound E: O H O

(c) An optically active compound F (C6H12), with an (S) absolute configuration, decolorizes a solution of Br2/CCl4. (2.5 marks) Compound F:

7.

A student attempted to synthesize compound H from benzene using alkyl chloride G and AlCl3 but compound I was obtained instead. Answer the following questions:
Cl G AlCl3 H (0%) (75%) Compound I

(a) Give the structure of Compound I and provide a mechanism to account for its formation. Answer:
H Cl + AlCl3 1,2-hydride shift 1o cation + AlCl 4 (not stable) 3o cation (more stable) H

(5 marks)

Cl AlCl3

+ HCl

+ AlCl3

(b) Compound H can be prepared by other methods (see Parts VII and IX of the lecture notes later in the course). Provide an efficient synthesis for the following transformation
? Br Br2 FeBr3 Br Br2, h Br Br NaOMe MeOH heat

(5 marks)

8.

Provide an efficient synthesis for each of the following transformations. Synthesis with the fewest steps, best yields and best selectivity will get maximum marks.
Br (a) (4 marks) O2N

Answer:

Br O2N Br2, FeBr3 Br conc. HNO3 conc. H2SO4 heat

(b)
(6 marks) Answer:

CH3 OCH3 OCH3

CH3 OCH3 OCH3 Br2 h Br NaOMe MeOH heat 1. NaH (2 equiv.) 2. CH3I (2 equiv.) 1. OsO4 2. NaHSO3 CH3 OH OH

(c) OH Answer: (6 marks) SCH3

OH TsCl pyridine NaI DMSO OTs I

SCH3 NaSCH3 DMSO

The above 8 questions add up to 100 marks. The following question on the next page is a Bonus Question (6 marks). Note: the maximum marks you can get for the exam is still 100 marks even if you answer all the questions (including the Bonus Question) correctly.

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Bonus Question:

Provide TWO different methods for the synthesis compound K from compound J. The first method using CH3I as the source of the CH3 group in compound K. The second method using CH3ONa as the source of the CH3 group in compound K. Synthesis with the fewest steps, best yields and best selectivity will get maximum marks.

Ph

Ph

(6 marks)

OCH3

Method 1: (CH3I as the source of the CH3 group) Answer:

Ph

Ph

OCH3

J
1. BH3 2. H2O2, NaOH Ph OH

K
1. NaH 2. CH3I

Method 2: (CH3ONa as the source of the CH3 group) Answer:

Ph

Ph

OCH3

J
HBr ROOR heat Ph Br

K
NaOCH3 DMSO

(END of EXAM)

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