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© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series
118 C Practice Syntheses Show how you would carry out the following synthesis using inorganic or organic reagents. Include the reagents you would need for each step and the structure of the intermediate products formed in each step. Some problems have more than one possible answer. Problems A-J approximately cover the reactions found in Volhardt+Schore chapters 19-21, problems K-AB cover approximately chapters 22,23, and problems AC-AI cover chapter 25.
OHA)
CrO3, H2O
H2SO4
OH
O
SOCl2
Cl
O
NH3NH2
O
Br2
NaOH, H2O
NH2
HN
O
CH3COCl,
TEA
TEA
Br
B)
KCN, DMF
CN Pd, H2CH2NH2
O
1)
2) NaBH3CN
HN
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series
OMs
C)
NaN3
DMF
N3 1) LiAlH4
2) H2O
or Pd, H2
NH2 O
Cl
pyridine
HN
O
1) LiAlH4
2) H2O
HN
1)
2) NaBH3CN
H
O
NH
O
O
D)
1) K2CO3
2)
Br
N
O
O
1) H2O, H2SO4, heat
2) NaHCO3, H2ONH2
O
1)
2) NaBH3CN
HN
Br2
HN
Br
Br
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series E)
OH
CrO3, H2OH2SO4
OH
O
Br2, P (trace) OH
O
BrKCN
DMFOH
O
CN
H2O, H2SO4
heat
OH
O
COOH
F)
Br
Mg,THF
MgBr1) CO2
2) H3O+COOH
CH3CH2OHH2SO4, heat
O
O
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series
Br
1) CH3COONa, DMF2) NaOH
HO
G)
PCC, CH2Cl2
orCrO3, H2SO4, H2O
OH
O
NH3
HCl, CH3CH2OH
1)
2) NaHCO3, H2O
O NH2
O
1)
2) NaBH3CN
O NH
OH
CrO3, H2O
H2SO4
OH
O
SOCl2
Cl
O
NH3NH2
O
1) LiAlH4
2) H2O
NH
CH3CH2COCl,
TEA
TEA
NH2
O
H)
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series I)
Br
KCN DMF
CNMgBr
1)
2) H3O+
O
NH2
1) NH3
2) NaBH3CN
J)
Br
KCNDMF
CN
H2SO4, H2Oheat
O
OH H2SO4,
CH3CH2OH O
O
1) CH3CH2CH2MgBr
(2eq)
2) H3O+
OH
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series
K)
Cl
HNO3 (2eq)H2SO4
Cl
NO2
NO2
KCN
CN
NO2
NO2
1) CH3CH2MgBr
2) H3O+
NO2
NO2
O
NH21)
2) NaBH3CN
NO2
NO2
HN
L)
HNO3
H2SO4
NO2
Zn(Hg), HCl
NH21) NaNO2, HCl2) CuI
I
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series
M)
Cl
1) NaOH, Heat
2) H3O+
OH
1) NaOH, CO2
2) H3O+
OH O
OH1) NaOH (1eq)
2) Br
OH O
O
CH3COCl
TEA
O O
O
O
N)
OH
OH
Na2Cr2O7
H2SO4
H2O
O
O
HCl
OH
OH
Cl
CrO3, H2O
H2SO4
O
O
Cl
2 eqheat
O
OCl
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series
O)
FeCl3Cl2
Cl NaNH2, NH3 NH2 1) NaNO2, HCl, 0oC
2) phenol
NN
OH
FeBr3Br2 (xs)
NN
OH
Br
Br
Br
Br
Br
P)
HNO3
H2SO4
NO2
Zn(Hg)
HCl
NH2
1) NaNO2, HCl, 0oC
2) CuCN
CN
FeCl3Cl2
CN
Cl
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series
Q)
HNO3
H2SO4
NO2
Zn(Hg)
HCl
NH2
1) NaNO2, HCl, 0oC
2) H2O
OH
1) NaOH, CO2, heat
2) H3O+
OH O
OH
1) H2SO4, CH3CH2OH
2) NaOHCH3I
OCH3O
OCH2CH3
R)
OH
1) NaOH2) Br
O
heat
OH
Br2
OH
Br
Br
1) NaNH2
2) H3O+
OH
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series
S)OCH3
OO
Br
NaOCH3
HOCH3
O
OCH3
O1) CH3ONa, CH3OH
2) O
O
COOCH3
H2, Pd/C
O
COOCH3
NH3
NaBH3CN
NH2
COOCH3
T)
OCH2CH3
O O
1) CH3CH2ONa,CH3CH2OH2)
Br
OCH2CH3
O O
CH3CH2OH
H2SO4
OCH2CH3
OO O
1)
2) H3O+
1) CH3CH2ONa,CH3CH2OH
2)Br
OCH2CH3
O O
MgBr (2 eq)
O OH
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series
U)
H H
O
HS SH
ZnCl2
S S
H H
1) CH3CH2CH2CH2Li
2)
3) H3O+H
O
S S
H OH
HgCl2
H2OH
O
OH
CrO3, H2SO4
H2OHO
O
O
1) SOCl2, pyridine2) CH3CH2OH
O
O
O
NaBH3CN
H2N
O
O
HN
V)
OCH3
O
CH3ONa
CH3OH
O O
OCH3
1) NaOCH3
2)
Br
O O
OCH3
H3O+
heat
O
NH
NaBH3CN
N
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series W)
O
O
O
1) NaOCH2CH3
HOCH2CH3
2)Cl
O
O
O1) NaOCH2CH3
HOCH2CH3
2) OTs
O
O
O
HCl, H2O
Heat
O
1) LiAlH4
2) H3O+
OH
X)HO OH
O O
H2SO4
CH3OH
H3CO OCH3
O O
1) CH3OH CH3ONa
2)Br
Cl
H3CO OCH3
O O
Cl
CH3ONa
CH3OHH3CO OCH3
O OHCl, H2Oheat
HO
O
1) SOCl2, pyridine2) NH3
H2N
O
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series
S SY)
1) nBu-Li2)
OMs
S S1) nBu-Li
2)
3) H3O+
OS S
HO
HgCl2, H2O
HO
O
Na2Cr2O7
H2SO4
H2O
HO
OO
Z)
H3CH2CO OCH2CH3
OO
1) NaOCH2CH3, HOCH2CH3
2)
O
H3CH2CO OCH2CH3
OO
O
H3O+, heat
HO
O O
1) NaOH
2) Br
O
O O
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series
AA)O
O O
O
O
OH
Na
O O
O
1) NaOCH2CH3
CH3CH2OH
2) Cl O O
OHCl, H2O
heat
O
NH2CH2CH3
NaBH3CN
HN
Cl
O
N
O
TEA
AB)OCH3
O
O
OCH3
CH3ONa
CH3OH
O O
OCH3
O
1) CH3ONa, CH3OH
2)
O O
OCH3
O
H2SO4, H2O
heat
O O
NaOCH3
HOCH3
Heat
O
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series AC)
N
NaNH2, NH3
N NH2
H
O
NaBH3CN N NH
Cl2 (2eq)
FeCl3
N NH
ClCl
AD)
HO
OH
PCC
CH2Cl2
H
O
O
P2S5,
heat S SO2N
HNO3
H2SO4
H2
Ni
SH2N
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series AE) H
N
KCNH2O
NCNH2 H2O, H2SO4, Heat NH3
O
HO
SOCl2Pyridine
NH
O
AF) O
H OCH3
O
O
H, NH3
N
COOCH3H3COOC
HNO3
N
COOCH3H3COOC 1) KOH
2) CaO, heatN N
Li
NaNH2
NH3
NH2N
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series AG)
O
O
Cl1)
AlCl3 (xs)
2) H3O+
O
OH
H3O+
heat
O
O
(2 eq)
OH
Pd H2
O
P2S5
heat
S
AH) O O
OCH3
CH2O, NH3
N
COOCH3H3COOC
HNO3 N
COOCH3H3COOC
1) KOH
2) CaO, heat N
HNO3
H2SO4 N
NO2
N
NH2
O
Cl
Zn(Hg)HCl, heat
N
HN
O
TEA
© S. Lievens April 2012 University of California, Davis For use with UCD Chem 118 Series AI)
HN
1) CH3CH2OH H2SO4
2) NaHCO3
H2NOCH2CH3
O
Cl NH
OCH2CH3
O
1) LiAlH4
2) H2O
NH
OCH2CH3
pyridine
