2886453 organic chemistry 342 reactions
TRANSCRIPT
©���� Gregory R� Cook page � Chem ��� Exam � ReactionsNorth Dakota State University
REACTIONSFor Final Exam
Reactions for Final Exam
Although you don’t need to know all of the mechanisms for these reactions, knowing themmakes it easier to understand the reactions and to figure out a reaction if you forget it. Consult thelecture notes for more details on the mechanisms and issues of stereo- and regioselectivity.
ELECTROPHILIC ADDITION REACTIONS
HX
X+
X
OCH3
HgO2CCF3
NaBH4
OCH3Hg(O2CCF3)2CH3OH
R R
OH
R
OHgSO4H3O+
enol ketone
CH3 CH3O
MCPBA
CH3 CH3OHBr
Br2H2O
CH3BH3H2O2, OH- CH3
HOH
CH3Hg(OAc)2 CH3
OHH2O
NaBH41)2)
CH3 OsO4 CH3OHNaHSO3OH
1)2)
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ELECTROPHILIC SUBSTITUTION REACTIONS
Br2FeBr3 Br
Cl2FeCl3 Cl
I2CuI2 I
HNO3H2SO4 NO2
SO3H2SO4 SO3H
R-ClAlCl3 R
R Cl
O
AlCl3 R
O
OBr2
CH3CO2H
OBr
Br2 PBr3O
OH
O
OH
1)
2) H2OBr
©���� Gregory R� Cook page � Chem ��� Exam � ReactionsNorth Dakota State University
NUCLEOPHILIC ADDITION REACTIONS
Ph H
O
Ph HHO CNHCN
cyanohydrinKOH
O HO OHH2O
hydrate
+
H+ or -OHcatalyst
OR-NH2
H+ N RH2O+ +
imine
OR2NH
H+ NRR
H2O+ +
enamine
O
ROHH+
RO OR
+ 2
an acetal
1,4-addition
OCH3NH2
O
NHCH3
1,4-addition
O O
Ph
1) Ph2CuLi2) H3O+
1,2-addition
O 1) PhMgBr2) H3O+ HO Ph
1,2-addition
O 1) PhLi2) H3O+ HO Ph
R Cl
OR Ph
1) PhMgBr2) H3O+ HO Ph
©���� Gregory R� Cook page � Chem ��� Exam � ReactionsNorth Dakota State University
R OCH3
OR Ph
1) PhMgBr2) H3O+ HO Ph
C N CH3
1) CH3MgBr2) H2O
O
O+ Ph3P CH2
phosphoniumylide
CH2 + Ph3P O
1,2-addition
O 1) NaBH42) H3O+ HO H
1,2-addition
O 1) LiAlH42) H3O+ HO H
The addition of hydrides to carbonyls is also considered reductions and more examples are listedunder reduction reactions.
O
OMgBr OH
OH3O+
MgBr
O C O
SUBSTITUTION REACTIONS (SN1)
CH3OH
HCl CH3O
H
H-H2O Cl
CH3
CH3O HCl
CH3
O HCl
OH
CH3Cl
(regioselective like SN1 but stereoselective like SN2) (also opens with water to make trans diol)
©���� Gregory R� Cook page � Chem ��� Exam � ReactionsNorth Dakota State University
SUBSTITUTION REACTIONS (SN2)
SO
Cl ClOHH S
O
O Cl Cl
PBr
Br BrOHH P
Br
O Br Br
SO
ClOH O Tos
Tos-Cl
pyridine
Br OH
Si ClCH3
H3CCH3
Br O Si CH3
CH3H3Cpyridine
trimethylsilyl chloride (TMS-Cl)
OH1) NaH
2) CH3IO CH3
O HI OH I OHI+
O HCl OH
ClCl
OH
O 1) PhMgBr
2) H2OPh
OH
Ph SHCH3I
Ph S CH3
R OH
O NaOH
R O
O
Na
CH3I
R OCH3
O
O 1) LDA2) CH3I
OCH3
©���� Gregory R� Cook page � Chem ��� Exam � ReactionsNorth Dakota State University
OEt
O
EtO
O NaOEt, EtOH
R BrOEt
O
EtO
O
R
OEt
O
H3C
O NaOEtEtOH
R BrOEt
O
H3C
O
R
SUBSTITUTION REACTIONS (Nucleophilic Aromatic and Nucleophilic Acyl)
Cl
NaOH
25 °C
O2N NO2
NO2
OHO2N NO2
NO2
NaOH
340 °C2500 psi
Cl OH
H H
benzyne intermediate
R OH
O+ SOCl2
R Cl
O+ SO2 + HCl
R OH
O+
R
O+ HOH
RHO
O Heat
RO
O
R OH
O HA
R'OH R OR'
O
R Cl
O+
R
O+ NaClRNaO
O
RO
O
R Cl
O+ H2O
R OH
O+ HCl
R Cl
O+ R'OH
R OR'
O+ Pyridine-HCl
pyridine
R Cl
O+ NH3 R NH2
O+ NH4Cl2
R Cl
O
R Ph
O1) Ph2CuLi2) H3O+
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+ H2OO
O O
OH
O2
+ ROHO
O O
OR
O+
OH
O
+ NH3O
O O
NH2
O+
OH
O
+R OCH3
O+ H2O
R ONa
ONaOH (cat)CH3OH
Ph H
HO C NH3O+
Ph H
HO CO
OH
R NH2
O+ H2O
R OH
OHA (cat)+ NH4A
CH3
OI2, NaOH
O
O
+ CHI3iodoform
ELIMINATION REACTIONS
OHH3C CH3H2SO4
E1
OHPOBr3pyridine
E2
NH2
OCl S Cl
O
C N
OBr pyridine
O
©���� Gregory R� Cook page Chem ��� Exam � ReactionsNorth Dakota State University
OXIDATION REACTIONS
R R
OH CrO3
H3O+ R R
O
R
OH CrO3
H3O+ R OH
O
PCCR
OH
R H
O
R
O CrO3
H3O+ R OH
O
H
R
O
R OH
O
H
Ag2ONH4OH
OKMnO4
O
OH
O
OH
OH
OKMnO4 2
O
H
O1) O32) Zn, AcOH +
Ph SH Ph S PhS
I2
PhS
CH3
H2O2Ph
SCH3
O
PhS
CH3
O OH3C OO
H
O
a sulfoxide a sulfone
KMnO4CH3 CO
OH
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KMnO4 CO
OH
KMnO4 CO
OH
O
REDUCTION REACTIONS
R OHR H
O1) NaBH42) H3O+
R OHR H
O1) LiAlH42) H3O+
R OHR OCH3
O1) LiAlH42) H3O+
R HR OCH3
O1) DIBAH2) H3O+ O
R HR C
1) DIBAH2) H3O+ O
N
1) LiAlH42) H3O+
Ph HHO C N
Ph HHO NH2
R OHR OH
O1) LiAlH42) H3O+
R OHR OH
O1) BH32) H3O+
©���� Gregory R� Cook page �� Chem ��� Exam � ReactionsNorth Dakota State University
R Cl
OR OH
1) LiAlH42) H3O+
R Cl
O
R H
O1) LiAlH(Ot-Bu)32) H3O+
R NH2R NH2
O1) LiAlH42) H2O
O H2N NH2
KOH
NNH2
a hydrazone
H H
Ph SHPh S PhSZn, H3O+
Pt, 2000 psi CH3
orRh/C, 15 psi
CH3
H2
Pd/C
O
H2
Pd/C
H2NO2Pd/C
NH2
SnCl2NO2 NH2H3O+
©���� Gregory R� Cook page �� Chem ��� Exam � ReactionsNorth Dakota State University
OTHER REACTIONS
NBSperoxides Br also benzylic
bromination
EWG+
EWG
KNH2Cl+ benzyne
intermediate
O O
H
OHheat
H3O+, Heat
HO
O
OEt
O
EtO
O
R
R + CO2
H3O+, Heat
OEt
O
H3C
O
R
H3C
O
R+ CO2