ether N D2O O Mg

CHE 325 ORGANOMETALLIC COMPOUNDS CHAP 14 ASSIGN
1. The final product, D, in the following reaction sequence,
CH 2 CH 2
CH 3 CHOH PBr 3
Mg
O
H 3 O +
A
B
C
D
ether
CH 3
, would be
CH 3 CHOCH 2 CH 2 OH CH 3 CHCH 2 CH 2 Br CH 3 CHCH 2 CH 2 OH CH 3 CHOCH 2 CH 3 CH 3 CHCH 2 CH 3
CH 3 CH 3 CH 3 CH 3 CH 3
A B C D E
2. What is the product, A, that would be obtained from the following reaction sequence
O
CH 3 CH 2 MgBr CH 3 CH CHCH 3
H 3 O +
C CH A
CH 3 CH 3
CHOCH 2 CH 3
C CCH
CH 3
CH 3
C CCH 2 CH 3 C CCH
CH 3 CH 2
CHOH
I II III
CH 3
CH 3
C
CCH
CH 3
C C CHCH 2 CH 3
CHOH
O
IV
A. I B. II C. III D. IV E. V
V
3. What would be the product, C, of the following reaction sequence
CH 3
CH 3 CCH 2 Br
Li
ether
A
CuI
B
CH 3
CH 3 CHCH 2 CH 2 Br
C
CH 3
A. 2,6-Dimethylheptane B. 2,2-Dimethylpropane
C. 2-Methylpentane D. 2,2,5-Trimethylhexane
E. 2,2,6-Trimethylheptane
4. What would be the product, O, of the following reaction sequence
CH 3 CH 2 CHCH 3 Mg
N
ether
Br
D 2 O
O
CH 3 CH 2 CHCH 3
A. CH 3 CH 2 CH 2 CH 3 B. D C.
D. CH 3 CH 2 CH 2 CH 2 OD E. CH 3 CH 2 CH 2 CH 2 D
1
CH 3 CH 2 CHCH 3
OD

5. What is the product, A, that would be obtained from the following reaction sequence
A. I
B. II
C. III
D. IV
E. V
OH
OH
PBr 3 Li (CH 3 ) 2 C=O NH 4 Cl
OH
10 o C
A
I
II
III
HO
IV
V
6. What would be the final product, A, in the following reaction sequence
A. I
B. II
C. III
D. IV
E. V
O
OH
O
PBr 3 Mg, Et 2 O H 3 O +
OH
heat
A
OH
I II III
Br
O
OH
IV
V
7. What would be the major product of the following reaction
A. (R)-3-ethyl-5-methylheptane
B. (R,S)-3-ethyl-5-methylheptane
C. (S)-3-ethyl-5-methylheptane
D. (3R,5S)-5-ethyl-3-methylheptane
E. (3S,5R)-5-ethyl-3-methylheptane
Cl
Li, Et 2 O
CuI
H
Br
CH 3
A
8. What is the principal product(s) formed when 1 mol of methylmagnesium iodide reacts with 1 mol of
p-hydroxyacetophenone
A. I
B. II
C. III
D. IV
E. V
IMgO
O
HO
CH 3 MgI
OMgI
+ CH 4 HO
O
I II III
O
O
A
O
O
O MgI IMgO
IV
V
2

OH H
9. What product(s) is/are produced in the 1:1 reaction of sec-butylmagnesium bromide with
CH 3 CHCH 2 CH 2 C
OH OMgBr
O
CH 3 CHCH 2 CH 2 CHCCH 2 CH 3
OMgBr
H
A.
CH 3 B.
CH 3 CHCH 2 CH 2 C
O + CH 3 CH 2 CH 2 CH 3
OH
OMgBr
OMgBr
H
C. CH 3CHCH 2 CH 2 CHCH 2 CH(CH 3 ) 2
H
D. CH 3CHCH 2 CH 2 C
O + (CH 3 ) 3 CH
CH 3 CHCH 2 CH 2 C
O
OCHCH 2 CH 3
E.
CH 3
10. What is the principal product of the following reaction:
O
CH 3 CH CH 2
CH 3 CHCH 2 CH 2 CH 2 CH 3
+ CH 3 CH 2 CH 2 CH 2 MgBr/ether; then H 2 O
OH
A)
CH 2 OH B. CH 3CHCH 2 CH 2 CH 2 CH 2 CH 3
OH
C. CH 3CHCH 2 OCH 2 CH 2 CH 2 CH 3
D.
CH 3 CHOCH 2 CH 2 CH 2 CH 3
CH 2 OH
CH 3 CHCH 2 OCH 2 CH 2 CH 2 CH 3
E.
OCH 2 CH 2 CH 2 CH 3
11. The reaction of lithium diethylcuprate with 1-bromo-4,4-dimethylhexane yields:
A. 3,3-Dimethylheptane B. 3,3-Dimethyloctane
C. 1-Ethyl-4,4-dimethylhexane D. Di-4,4-dimethylhexylcuprate
E. None of the above
12. Which of the following synthetic procedures would be employed most effectively to transform ethanol into ethyl propyl
ether
A. Ethanol + HBr, then Mg/ether, then H 3 O + , then NaH, then CH 3 CH 2 Br
B. Ethanol + HBr, then Mg/ether, then HCHO, then H 3 O + , then NaH, then CH 3 CH 2 Br
C. Ethanol + CH 3 CH 2 CH 2 OH + H 2 SO 4 /140C
D. Ethanol + NaH, then HCHO, then H 3 O + , then HBr, then Mg/ether, then CH 3 CH 2 CH 2 Br
E. Ethanol + H 2 SO 4 /180°C, then CH 3 CH 2 CH 2 Br
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13. What compound(s) result(s) from the reaction of CH 3 CH 2 CH 2 MgBr with CH 3 CH 2 CH 2 CH 2 CO 2 H (1:1 mole ratio)
(CH 3 CH 2 CH 2 ) 2 CCH 2 CH 2 CH 2 CH 3
O
A.
OH B. CH 3CH 2 CH 2 CCH 2 CH 2 CH 2 CH 3
O
C. CH 3CH 2 CH 2 CH 2 COCH 2 CH 2 CH 3
D. CH 3 CH 2 CH 3 + CH 3 CH 2 CH 2 CH 2 CO 2 MgBr
O
O
E. CH 3CH 2 COCCH 2 CH 2 CH 2 CH 3
C 6 H 5
CH 3 CH 2 CH 2 CCH 3
14. Your task is to synthesize
OH through a Grignard synthesis. Which pairs of compounds listed below
would you choose as starting materials
O
O
A.
CH 3 CH 2 CH 2 Br and
CH 3 CC 6 H 5
B. CH 3CH 2 CH 2 CH and C 6 H 5 Br
O
C. C 6H 5 CH
and
CH 3 CH 2 CHCH 3
Br
D. More than one of these. Which ones
E. None of these
15. Your task is to synthesize 2-phenyl-2-hexanol through a Grignard synthesis. Which pair(s) of compounds listed below
would you choose as starting materials
A.
CH 3 CH 2 CH 2 Br and
O
O
CH 3 CC 6 H 5
B.
CH 3 CHCH 2 Br
CH 3
and
O
CH 3 CC 6 H 5
C. CH 3CH 2 CH 2 CH 2 CCH 3 and C 6 H 5 Br
D. Answers A or B
E. Answers A or C
16. Which combination of reagents is to be preferred for the synthesis of 2,4-dimethylhexane by the Corey-Posner,
Whitesides-House procedure
A. Lithium diisobutylcuprate + sec-butyl bromide
B. Lithium dimethylcuprate + 2-bromo-4-methylhexane
C. Lithium dimethylcuprate + 4-bromo-2-methylhexane
D. Lithium diisopropylcuprate + 1-bromo-2-methylbutane
E. Lithium di(2-methylbutyl)cuprate + isopropyl bromide
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17. Which of the following would serve as a synthesis of racemic 2-methyl-1-phenyl-2-butanol
A. I
B. II
C. III
D. All of the above
E. None of the above
CH 3
OH
CCH 2 CH 3
CH 2 MgCl
I
CH 3 CH 2 CCH 3
1. Et 2 O
+
O 2. NH
+ 4
II
O
CH 2 CCH 3
+ CH 3 CH 2 MgBr
1. Et 2 O
2. NH 4
+
III
CH 2 CCH 2 CH 3
O
+ CH 3 MgI
1. Et 2 O
2. NH 4
+
18. Which Grignard synthesis will produce an optically active product or product mixture
MgBr
A.
+
O
+ ClMg
O
B.
C.
O
O
+
MgI
D.
O
+
H CH 3
MgI
E. O
H 3 C
H
+
MgBr
19. Which of the following is the strongest acid
A. RMgX B. Mg(OH)X C. RH D. H 2 O
20. Which of the following is the strongest base
A. RMgX B. Mg(OH)X C. RH D. H 2 O
21. Grignard reagents react with oxirane (ethylene oxide) to form 1 alcohols but can be prepared in tetrahydrofuran solvent.
Why is this difference in behavior observed
A. Steric hindrance in the case of tetrahydrofuran precludes reaction with the Grignard.
B. There is a better leaving group in the oxirane molecule.
C. The oxirane ring is the more highly strained.
D. It is easier to obtain tetrahydrofuran in anhydrous condition.
E. Oxirane is a cyclic ether, while tetrahydrofuran is a hydrocarbon.
22. Which of these compounds can be used to prepare the corresponding Grignard reagent
A. CH 3 CHOHCH 2 CH 2 CH 2 CH 2 Br
B. (CH 3 ) 3 CHCHBrCH 2 CH 2 CO 2 H
C. BrCH=CHCH 2 CH 2 CH 3
D. CH 3 NHCH 2 CH 2 Br
E. None of the above can be used to prepare the corresponding Grignard reagent
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23. Which of these compounds cannot be used to prepare the corresponding Grignard reagent
A. CH 3 OCH 2 CH 2 CH 2 Br B. (CH 3 ) 3 CCl
C. CH 2 =CHCH 2 Br D. (CH 3 ) 2 NCH 2 CH 2 Br
H
E. O CCH 2 CH 2 I
24. Which of these is the least reactive type of organometallic compound
A. RK B. R 2 Hg C. RLi D. R 2 Zn E. R 3 Al
25. If the role of the solvent is to assist in the preparation and stabilization of the Grignard reagent by coordination with the
magnesium, which of these solvents should be least effective
A. I
B. II
C. III
D. IV
E. V
CH 3 CH 2 OCH 2 CH 3
O
(CH 3 CH 2 ) 3 N
I II III
CH 3 (CH 2 ) 4 CH 3 CH 3 OCH 2 CH 2 OCH 3
IV
V
26. Which of these is most likely to be a successful synthesis of an organometallic compound
A. CH 3 CH 2 CH 2 MgBr + LiCl CH 3 CH 2 CH 2 Li + MgBrCl
B. 2 CH 3 CH 2 CH 2 CH 2 Li + ZnCl 2 (CH 3 CH 2 CH 2 CH 2 ) 2 Zn + 2 LiCl
C. 3 (CH 3 CH 2 ) 2 Hg + 2 AlCl 3 2 (CH 3 CH 2 ) 3 Al + 3 HgCl 2
D. (CH 3 CH 2 ) 3 Al + 3 NaCl 3 CH 3 CH 2 Na + AlCl 3
E. (CH 3 ) 2 Cu + MgBr 2 (CH 3 ) 2 Mg + CuBr 2
27. What is the product of the following reaction
1) HO
OH 3)
O
OH
OH
O
1) 2 CH 3 MgBr
2) H 3 O +
2) OH 4)
OH
28. 1-Phenylnaphthalene, shown below, can be prepared in over 80% yield by one of the reactions below. Which one
Br
C 6 H 6 , AlCl 3
1) 3)
I
(C 6 H 5 ) 2 CuLi
2) 4)
diethyl ether
Cl
C 6 H 5 MgBr
diethyl ether
C 6 H 5 Br, AlCl 3
C 6 H 5
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NAME_______________________________________
DATE______________
ANSWER SHEET
CHE 325 – CHAP 14 ASSIGN
1. _______________ 13. _______________ 25. _______________ 37. _______________
2. _______________ 14. _______________ 26. _______________ 38. _______________
3. _______________ 15. _______________ 27. _______________ 39. _______________
4. _______________ 16. _______________ 28. _______________ 40. _______________
5. _______________ 17. _______________ 29. _______________ 41. _______________
6. _______________ 18. _______________ 30. _______________ 42. _______________
7. _______________ 19. _______________ 31. _______________ 43. _______________
8. _______________ 20. _______________ 32. _______________ 44. _______________
9. _______________ 21. _______________ 33. _______________ 45. _______________
10. _______________ 22. _______________ 34. _______________ 46. _______________
11. _______________ 23. _______________ 35. _______________ 47. _______________
12. _______________ 24. _______________ 36. _______________ 48. _______________
SS II 2013
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