Embed Size (px)
Citation preview
Exploration of a Selective Aerobic
Oxygenation Reaction
William GuyStahl Lab
Background Selective Oxidation with O2
Green, Abundant, Inexpensive
Uncontrolled Oxidation: Combustion
Goal is to find ways to control reactivity of O2
Controlled with catalysts
Electron Withdrawing Group
SelectivityControl of reactivity of O2
~88 kcal/mol~104 kcal/mol
~88 kcal/mol
NHPI (n-hydroxylphthalimide)
~100 kcal/mol
Ethylbenzene
Fox,T.;Kollman,P. C-H Bond Dissociation Energies in Toluene, 1996 100, 2950-2956Lao,Yu-Ran; Handbook of Bond Dissociation Energies, 2003, 3.1,3.4
NHPI PINO
Studied Reaction Selective NHPI-mediated aerobic oxidation of ethylbenzene was
explored
A series of activators was screenedeg: Mn2+, Mn4+, Co2+, Pt2+
Ethylbenzene NHPI
PINOAcetophenone
Data
Activator Ethylbenzene Ketone Alcohol
AcOH, NHPI Ctrl 79 9 0
No NHPI, PtC AcOH 78 0.1 0.1
Pt GraphC AcOH 56 26 7
PtBiC AcOH 50 24 8
PtC Supp AcOH 74 9 2
Synthesized PtC AcOH 55 26 10
• O2 known to oxidize Pt well
Data
Activator Ethylbenzene Ketone Alcohol
AcOH, NHPI Ctrl 79 9 0
No NHPI, PtC AcOH 78 0.1 0.1
Pt GraphC AcOH 56 26 7
PtBiC AcOH 50 24 8
PtC Supp AcOH 74 9 2
Synthesized PtC AcOH 55 26 10
• O2 known to oxidize Pt well
Data
Activator Ethylbenzene Ketone Alcohol
NHPI Cntl (No Mn) 74 20 3
MnO 25 53 6
MnO2 29 46 4
Mn2O3 36 45 5
Mn3O4 28 53 5
Mn(OAc)2 25 53 5
• All Mn activators performed similarly
• MnxOx surrogate to Mn(OAc)2
Jiang,J; Jing,Y; Zhang,Y; Jiao,J; Oxidation of Toluene, 2010
Data
Activator Ethylbenzene Ketone Alcohol
NHPI Cntl (No Mn) 74 20 3
MnO 25 53 6
MnO2 29 46 4
Mn2O3 36 45 5
Mn3O4 28 53 5
Mn(OAc)2 25 53 5
• All Mn activators performed similarly
• MnxOx surrogate to Mn(OAc)2
Jiang,J; Jing,Y; Zhang,Y; Jiao,J; Oxidation of Toluene, 2010
Data
Activator Ethylbenzene Ketone Alcohol
Control (NHPI) 83 14 3
Control (Co) 88 12 1
Co(OAc)2 19 73 2
Co(OAc)2 w/ MCBA 6 100 1
Co3O4 nanoparticles (commercial) 76 18 2
Co3O4 nanoparticles (synthesized) 51 41 6
Beller Co/CN catalyst 51 41 6
• Co(OAc)2 w/ MCBA has best yield
• Co3O4 nanoparticles vs. Beller catalyst
Ishii,Y; Catalytic Oxidation,J. Org. Chem, 1997 62, 6810-6813
Data
Activator Ethylbenzene Ketone Alcohol
Control (NHPI) 83 14 3
Control (Co) 88 12 1
Co(OAc)2 19 73 2
Co(OAc)2 w/ MCBA 6 100 1
Co3O4 nanoparticles (commercial) 76 18 2
Co3O4 nanoparticles (synthesized) 51 41 6
Beller Co/CN catalyst 51 41 6
• Co(OAc)2 w/ MCBA has best yield
• Co3O4 nanoparticles vs. Beller catalyst
Ishii,Y; Catalytic Oxidation,J. Org. Chem, 1997 62, 6810-6813
Data
Activator Ethylbenzene Ketone Alcohol
Control (NHPI) 83 14 3
Control (Co) 88 12 1
Co(OAc)2 19 73 2
Co(OAc)2 w/ MCBA 6 100 1
Co3O4 nanoparticles (commercial) 76 18 2
Co3O4 nanoparticles (synthesized) 51 41 6
Beller Co/CN catalyst 51 41 6
• Co(OAc)2 w/ MCBA has best yield
• Co3O4 nanoparticles vs. Beller catalyst
Ishii,Y; Catalytic Oxidation,J. Org. Chem, 1997 62, 6810-6813
ConclusionSome success with new activators
Mn activatorsLiterary work still performs bestThanks to Damian, the Stahl Lab, Professor Cui
References Fox,T.;Kollman,P. C-H Bond Dissociation Energies in Toluene,
1996 100, 2950-2956
Ishii,Y; Catalytic Oxidation,J. Org. Chem, 1997 62, 6810-6813
Einhorn,C; Einhorn,J; Marcadal,C; Oxidation of Organic Substraits, Chem Community, 1996
Sung,S.K.; Rajagopal, G; Efficient Aerobic Oxidation, Inha University, 2006, 402-751
Jiang,J; Jing,Y; Zhang,Y; Jiao,J; Oxidation of Toluene, 2010
Lao,Yu-Ran; Handbook of Bond Dissociation Energies, 2003, 3.1,3.4
