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Bài tập hóa hữu cơ: cơ chế và phản ứng carbonyl môn Cơ sở lý thuyết Hoá Học | Trường Đại học Sư phạm Thành phố Hồ Chí Minh

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Môn: Cơ sở lý thuyết Hoá Học 15 tài liệu

Trường: Đại học Sư phạm Thành phố Hồ Chí Minh 159 tài liệu

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Danh sách Quiz
/9
lOMoARcPSD| 22014077
2
lOMoARcPSD| 22014077
Chemistry 234
Synthetic Transformations of Carbonyl Compounds –
Problem Set
Reduction Reactions
1) Predict the product for each
reaction shown below.
O 1. LiAlH
4
2. H O
H
NaBH
4
4
O CH
3
OH
+
4
Cl 3
O 1. LiAlH
4
4
O 2. H
3
O
1. DIBAL-H
-78 ¡C
Cl 2. H
2
O
1. DIBAL-H
O -78 ¡C
O 2. H O
2) Predict the product for each reduction reaction below. Pay close
attention to chemoselectivity.
O O NaBH
4
OCH
3
CH
3
OH
3
+
+
NH
2
O
OH
OH
O
NH
O
1
. LiAlH
. H
2
3
O
. LiAlH
1
. H
2
3
O
+
NaBH
CH
3
OH
. LiAlH
1
4
2
. H
3
O
+
1
. LiAlH
4
2
. H
3
O
+
O
NaBH
4
CH
3
OH
O
1
. LiAlH
4
2
. H
+
O
lOMoARcPSD| 22014077
O 1. DIBAL-H
OH -78 ¡C
Cl2. H
2
O
O
O
NaBH
4
CH
3
OH
O
Oxidation Reactions
3) Predict the product for each reaction below. Assume an
excess of oxidizing agent is present.
OH
PCCPCC
HO
OH
Na2Cr2O7Na2Cr2O7
H
HO
2
SO
4
H H2SO4
OH Na
2
Cr
2
O
7
Na2Cr2O7
H
2
SO
4
OH H2SO4
Addition of Organometallic Reagents (Grignard, Lithiates, and
Acetylide ions)
4) Predict the product for each reaction shown below. Assume an
excess of organometallic reagent.
O
H
3
CMgBr
1.
2
. H
3
+
N
O
O
HO
lOMoARcPSD| 22014077
H 3
Cl
3
C Li 1. H
2. H
3
O
+
O
O
1. H
3
C MgBr
O 2. H
3
O
+
O
2. H
3
O
+
OH 1.
H
3
C Li
1. Mg
Br 2. O
3. H
3
O
+
Addition of Organometallic Reagents
(Organocuprates) 5) Predict the product for
each reaction shown below.
O
O
O
OCH
3
2. H
3
O
+
2. H
3
O
+
Ph
MgBr
1.
2
. H
O
+
Ph
Na
1.
MgBr
1.
1
. Ph
2
CuLi
2
. H
2
O
1
. Ph
2
CuLi
2
. H
O
lOMoARcPSD| 22014077
O
2
O
Cl
O 2. H
2
O
6) What reagent is needed to convert propanoyl chloride to
each of the following?
HPh
O O OH
Ph
OH
7) Draw the electron pushing mechanism for the addition of
methyl cuprate to 3-buten-2-one.
O 1. Me
2
CuLi
2. H O
H
1
. (CH
3
)
2
CuLi
2
. H
2
O
O
1
. (CH
3
)
2
CuLi
2
. H
2
O
O
1
. (CH
3
)
2
CuLi
2
lOMoARcPSD| 22014077
Protecting Groups in Organic Synthesis
8) Propose how you could carry out the following synthetic sequence.
Hint: PBr
3
converts alcohols to bromides.
O?
OHOH
9) A student tried to carry out the reaction sequence below, but
none of the diol (A) was formed. Explain what went wrong
with the plan and design a
successful synthesis of A.
Mg
OH OH
BrBrMgOH
A
General Mechanisms
10) Draw the electron pushing mechanism for each reaction shown
below.
O
OH
Br
O
2
. H
3
O
+
1.
OH
O
H
3
CMgBr
1.
2
. H
3
O
+
OH
lOMoARcPSD| 22014077
OH
+ CH
3
OH + (CH
3
)
3
COH
O O
OH
+ 2 CH
3
OH
Synthesis
11) Consider the following reaction sequence. Identify the missing
reagents.
O
H
3
CMgBr
1.
2
. H
3
O
+
(
excess
)
O
O
BrMg
MgBr
followed by dilute H
+
lOMoARcPSD| 22014077
OHO 1. CH
3
MgBr
+
OH
2. H
3
O
OH
1. PhMgBr
Ph O
2. H
3
O
lOMoARcPSD| 22014077
Ph
12) Provide a reasonable synthetic route to carry out the synthetic
transformation shown below.
O ? O Ph
H Ph
13) Design a reasonable synthesis for each of the following using
the provided starting materials.
Unless otherwise specified, you may use any other organic or
inorganic reagents as necessary.
HO
O ?
OCH
3
OH OH
?
Br
Ph
(these are your only
allowed sources of carbon)
Ph
Ph
lOMoARcPSD| 22014077
O O CH
3
?
Br
H BrH3C
(these are your only allowed
sources of
carbon)
14) Challenge Question: Show how 2-hexanone could be synthesized using
only ethanol and any other inorganic reagents. Hint: you might
need to use a couple of reactions from organic 1.

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lOMoAR cPSD| 22014077 lOMoAR cPSD| 22014077 Chemistry 234
Synthetic Transformations of Carbonyl Compounds – Problem Set Reduction
Reactions 1) Predict the product for each reaction shown below. O NaBH 4 O 1. LiAlH4 CH 3 OH 3 + 2. H O NH 2 1 . LiAlH O . H 2 3 O H NaBH4 4 O CH3OH + O 1. L iAlH O 1 . LiAlH 4 OH . H 2 3 O + 2 . H O + 4 Cl 3 O NaBH OH CH 3 OH O 1. LiAlH4 4 O + O 2. H3O 1. L iAlH 4 O O 2 . H 3 O + 1. DIBAL-H -78 ¡C O 1 . LiAlH Cl 2. H 4 2O NH 2 . H 3 O + 1. DIBAL-H O -78 ¡C O 2. 2 H O 2) Predict the product for each reduction reaction below. Pay close attention to chemoselectivity. O O NaBH4 OCH3 CH3OH lOMoAR cPSD| 22014077 O 1. DIBAL-H OH -78 ¡C Cl2. H2O O O NaBH4 N CH3OH O Oxidation Reactions 3) Predict the product for each reaction below. Assume an excess of oxidizing agent is present. O OH PCCPCC HO O OH Na2Cr2O7Na2Cr2O7 H HO HO2SO4H H2SO4 OH Na2Cr2O7Na2Cr2O7 H2SO4 OH H2SO4 Addition of Organometallic Reagents
(Grignard, Lithiates, and Acetylide ions) 4) Predict the product for each reaction shown below. Assume an excess of organometallic reagent. O 1. H 3 CMgBr 2 . H 3 O + lOMoAR cPSD| 22014077 O 1. Ph MgBr 2 . H O + H 3 Cl 3C Li 1. H 2. H3O+ O O 1. H3C MgBr O 2. H3O+ 1. Ph Na O 2. H3O+ OH 1. H3C Li O 2. H3O+ 1. MgBr O OCH3 2. H3O+ 1. Mg Br 2. O 3. H3O+ Addition of Organometallic Reagents
(Organocuprates) 5) Predict the product for each reaction shown below. 1 . Ph 2 CuLi 2 . H 2 O O 1 . Ph 2 CuLi 2 . H O lOMoAR cPSD| 22014077 O 2 1 . (CH 3 ) 2 CuLi H 2 . H 2 O O O 1 . (CH 3 ) 2 CuLi 2 . H 2 O Cl O 1 . (CH 3 ) 2 CuLi O 2. H2O 6) What reagent is needed to convert propanoyl chloride to each of the following? HPh Ph O O OH OH 7) Draw the electron pushing mechanism for the addition of methyl cuprate to 3-buten-2-one. O 1. Me2CuLi 2. H O 2 lOMoAR cPSD| 22014077
Protecting Groups in Organic Synthesis 8) Propose how you could carry out the following synthetic sequence. Hint: PBr3 converts alcohols to bromides. O? Br OHOH 9) A student tried to carry out the reaction sequence below, but none of the diol (A) was formed. Explain what went wrong with the plan and design a successful synthesis of A. 1. O OH Mg 2 . H 3 O + OH OH BrBrMgOH A General Mechanisms 10) Draw the electron pushing mechanism for each reaction shown below. O 1. H 3 CMgBr OH O 2 . H 3 O + OH lOMoAR cPSD| 22014077 OH O 1. H 3 CMgBr O ( excess ) + CH3OH + (CH3)3COH 2 . H 3 O + OH O O MgBr O O BrMg + 2 CH3OH followed by dilute H + O O Synthesis 11) Consider the following reaction sequence. Identify the missing reagents. lOMoAR cPSD| 22014077 OHO 1. CH3MgBr+ OH 2. H3O OH 1. PhMgBr Ph O 2. H3O lOMoAR cPSD| 22014077 Ph 12) Provide a reasonable synthetic route to carry out the synthetic transformation shown below. O ? O Ph H Ph 13) Design a reasonable synthesis for each of the following using the provided starting materials. Unless otherwise specified, you may use any other organic or inorganic reagents as necessary. HO O ? Ph OCH3 OH OH ? Br Ph Ph (these are your only allowed sources of carbon) lOMoAR cPSD| 22014077 O O CH3 Br ? H BrH3C (these are your only allowed sources of carbon) 14) Challenge Question: Show how 2-hexanone could be synthesized using only ethanol and any other inorganic reagents. Hint: you might need to use a couple of reactions from organic 1.

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