Lecture Slides • Spring 2009
Lecture 1: January 13, 2009
Main topics include:
• Syllabus
• i>clicker & OWL registration
• website
• define organic chemistry
• orbitals (Schrodinger equation)
• valence electrons
• models of bonding
• bond-line formulas
Main topics include:
• Syllabus
• i>clicker & OWL registration
• website
• define organic chemistry
• orbitals (Schrodinger equation)
• valence electrons
• models of bonding
• bond-line formulas
The
following slides were presented during lecture on
the dates indicated. These slides are only made
available after
the
indicated lecture date. Every effort is made to
correct errors found on slides during lecture
before posting. i>Clicker questions may also be
found within the slides in the order they were
presented during lecture. Alternatively,
i>clicker questions, correct answers and
statistics can be found of the i>clicker
page.
Lecture 2: January 15, 2009
Main topics include:
• electron configuration
• formal charge
• VSEPR
• resonance
• curved arrow notation
• structural effects on acid strength
• electronegativity (periods)
• bond strength (groups)
• resonance
Main topics include:
• electron configuration
• formal charge
• VSEPR
• resonance
• curved arrow notation
• structural effects on acid strength
• electronegativity (periods)
• bond strength (groups)
• resonance
Lecture 3: January 20, 2009
Main topics include:
• acidity/pKa
• classes of hydrocarbons
• alkanes
• valence bond model
• sp3 hybridization
• sigma bonds
• nomenclature of alkanes
Main topics include:
• acidity/pKa
• classes of hydrocarbons
• alkanes
• valence bond model
• sp3 hybridization
• sigma bonds
• nomenclature of alkanes
Lecture 4: January 22, 2009
Main topics include:
• nomenclature of cycloalkanes
• physical properties of alkanes
• boiling points of alkanes
• van der Waals forces (London disp.)
• chemical properties of alkanes
• acidities of alkanes
• combustion
• oxidation/reduction on carbon
• sp2 hybridization in alkenes
Main topics include:
• nomenclature of cycloalkanes
• physical properties of alkanes
• boiling points of alkanes
• van der Waals forces (London disp.)
• chemical properties of alkanes
• acidities of alkanes
• combustion
• oxidation/reduction on carbon
• sp2 hybridization in alkenes
Lecture 5: January 27, 2009
Main topics include:
• isomers classification
• conformations of alkanes
• drawing conformations: Newman projections, sawhorse, dash & wedge
• steric vs. hyperconjugation argument
• heats of combustion of cycloalkanes
• conformations of cyclopropane, cyclobutane, and cyclopentane
Main topics include:
• isomers classification
• conformations of alkanes
• drawing conformations: Newman projections, sawhorse, dash & wedge
• steric vs. hyperconjugation argument
• heats of combustion of cycloalkanes
• conformations of cyclopropane, cyclobutane, and cyclopentane
Lecture 6: January 29, 2009
Main topics include:
• summary of strain types
• quantitative energy costs for various conformational relationships
• chair & boat conformations for cyclohexane (axial & equatorial bonds)
• mechanism of ring inversion
• drawing cyclohexane rings
• conformational analysis for mono and disubstituted cyclohexanes (1,3-diaxial)
Main topics include:
• summary of strain types
• quantitative energy costs for various conformational relationships
• chair & boat conformations for cyclohexane (axial & equatorial bonds)
• mechanism of ring inversion
• drawing cyclohexane rings
• conformational analysis for mono and disubstituted cyclohexanes (1,3-diaxial)
Lecture 7: February 3, 2009
Main topics include:
• equilibrium and free energy
• configurational vs. constitutional
• functional groups
• naming alcohols and alkyl halides
• physical properties of alcohols
• physical properties of alkyl halides
• preparation of alkyl halides
• reactivity
• alternative conditions & reagents
Main topics include:
• equilibrium and free energy
• configurational vs. constitutional
• functional groups
• naming alcohols and alkyl halides
• physical properties of alcohols
• physical properties of alkyl halides
• preparation of alkyl halides
• reactivity
• alternative conditions & reagents
Lecture 8: February 5, 2009
Main topics include:
• substitution reactions
• mechanisms: SN1, SN2
• carbocations
• inductive effect & hyperconjugation
• transition states
• rate laws for rate determining step
• halogenation of alkanes
• selectivity of halogenation
• Hammond Postulate
Main topics include:
• substitution reactions
• mechanisms: SN1, SN2
• carbocations
• inductive effect & hyperconjugation
• transition states
• rate laws for rate determining step
• halogenation of alkanes
• selectivity of halogenation
• Hammond Postulate
Lecture 9: February 10, 2009
Main topics include:
• electromagnetic radiation
• energy gap comparison for spectroscopic techniques
• infrared spectroscopy
Main topics include:
• electromagnetic radiation
• energy gap comparison for spectroscopic techniques
• infrared spectroscopy
Lecture 10: February 12, 2009
Main topics include:
• mass spectrometry
• mass spectrometer
• molecular ions, fragmentation
• isotopic clusters
• nuclear magnetic resonance (NMR)
• nuclear spin states
• NMR spectrometer
• shielding
• chemical shift
Main topics include:
• mass spectrometry
• mass spectrometer
• molecular ions, fragmentation
• isotopic clusters
• nuclear magnetic resonance (NMR)
• nuclear spin states
• NMR spectrometer
• shielding
• chemical shift
Lecture 11: February 17, 2009
Main topics include:
• equivalent sets of protons
• integration
• multiplicity
• vicinal and geminal coupling
• origin of spin-spin splitting (coupling)
• splitting patterns and peak intensities
• measuring coupling constants
• NMR examples
Main topics include:
• equivalent sets of protons
• integration
• multiplicity
• vicinal and geminal coupling
• origin of spin-spin splitting (coupling)
• splitting patterns and peak intensities
• measuring coupling constants
• NMR examples
Lecture 12: February 19, 2009
Main topics include:
• complex splitting patterns
• distortion of peak intensities
• 13C-NMR spectroscopy
• DEPT
• Index of Hydrogen Deficiency
• Additional NMR Resources
Main topics include:
• complex splitting patterns
• distortion of peak intensities
• 13C-NMR spectroscopy
• DEPT
• Index of Hydrogen Deficiency
• Additional NMR Resources
Lecture 13: February 24, 2009
Main topics include:
• more NMR practice
• alkenes/olefins
• IHD review
• alkene/alkenol nomenclature
• structure/bonding of double bonds
• barrier to rotation
• geometrical isomers: cis & trans
• CIP rules for prioritizing groups
• B-eliminations introduction; dehyd.
Main topics include:
• more NMR practice
• alkenes/olefins
• IHD review
• alkene/alkenol nomenclature
• structure/bonding of double bonds
• barrier to rotation
• geometrical isomers: cis & trans
• CIP rules for prioritizing groups
• B-eliminations introduction; dehyd.
Lecture 14: February 26, 2009
Main topics include:
• dehydration regioselectivity (Zaitsev)
• dehydration stereoselectivity
• E1 & E2 mechanisms
• rearrangements
• dehydrohalogenation
• conditions/alkoxides
• E2 mechanism (anti elimination)
• anti E2 (molecular orbital argument)
• anti E2 (conformational argument)
Main topics include:
• dehydration regioselectivity (Zaitsev)
• dehydration stereoselectivity
• E1 & E2 mechanisms
• rearrangements
• dehydrohalogenation
• conditions/alkoxides
• E2 mechanism (anti elimination)
• anti E2 (molecular orbital argument)
• anti E2 (conformational argument)
Lecture 15: March 3, 2009
Main topics include:
• addition reactions to alkenes
• hydrogenation: conditions, syn add.
• heat of hydrogenation
• Markovnikov addition of HX
• mechanistic explanation for Mark.
• peroxide effect on HBr addition
• H2SO4 and H2O addition
• microscopic reversibility
• intro to synthesis
Main topics include:
• addition reactions to alkenes
• hydrogenation: conditions, syn add.
• heat of hydrogenation
• Markovnikov addition of HX
• mechanistic explanation for Mark.
• peroxide effect on HBr addition
• H2SO4 and H2O addition
• microscopic reversibility
• intro to synthesis
Lecture 16: March 5, 2009
Main topics include:
• hydroboration-oxidation (syn add.)
• regioselectivity of and mechanism
• halide addition to alkenes
• stereoselectivity of halide add. (anti addition; halohydrins & regioselect.)
• epoxidation
• ozonolysis
• synthesis; retrosynthesis
Main topics include:
• hydroboration-oxidation (syn add.)
• regioselectivity of and mechanism
• halide addition to alkenes
• stereoselectivity of halide add. (anti addition; halohydrins & regioselect.)
• epoxidation
• ozonolysis
• synthesis; retrosynthesis
Lecture 17: March 10, 2009
Main topics include:
• mirror images
• chirality: chiral objects
• chirality center: chiral molecules
• achiral test: plane of symmetry
• achiral test: center of symmetry
• R/S notation based on CIP rules
• optical isomers: enantiomers
Main topics include:
• mirror images
• chirality: chiral objects
• chirality center: chiral molecules
• achiral test: plane of symmetry
• achiral test: center of symmetry
• R/S notation based on CIP rules
• optical isomers: enantiomers
Lecture 18: March 12, 2009
Main topics include:
• IUPAC nomenclature of stereoisomers
• drawing Fisher projections
• properties of enantiomers
• optical rotation (enantiomeric excess)
• diastereomers & meso forms
• determining # of stereoisomers
• reactions that create chirality center
• stereospecific vs. stereoselective
Main topics include:
• IUPAC nomenclature of stereoisomers
• drawing Fisher projections
• properties of enantiomers
• optical rotation (enantiomeric excess)
• diastereomers & meso forms
• determining # of stereoisomers
• reactions that create chirality center
• stereospecific vs. stereoselective
Lecture 19: March 17, 2009
Main topics include:
• nucleophilic substitution
• nucleophiles & electrophiles
• reactivity of halide leaving groups
• review: SN2 of alcohols by halides
• SN2 mechanism
• inversion of configuration
• backside attack (molecular orbitals)
• stereospecific SN2 reactions
• steric effects & nucleophilicity
Main topics include:
• nucleophilic substitution
• nucleophiles & electrophiles
• reactivity of halide leaving groups
• review: SN2 of alcohols by halides
• SN2 mechanism
• inversion of configuration
• backside attack (molecular orbitals)
• stereospecific SN2 reactions
• steric effects & nucleophilicity
Lecture 20: March 19, 2009
Main topics include:
• non-nucleophilic bases
• SN1 mechanism
• solvolysis
• carbocation stability (review)
• rate of SN1 & SN2: solvent effects
• stereochemistry of SN1
• Elimination-Substitution competition
• conditions favoring substitution
• Alkyl sulfonates as leaving groups
Main topics include:
• non-nucleophilic bases
• SN1 mechanism
• solvolysis
• carbocation stability (review)
• rate of SN1 & SN2: solvent effects
• stereochemistry of SN1
• Elimination-Substitution competition
• conditions favoring substitution
• Alkyl sulfonates as leaving groups
Lecture 21: March 31, 2009
Main topics include:
• Substitution/Elimination review
• alkynes: nomenclature
• structure of alkynes, review
• bonding/hybridization, review
• terminal alkynes as acids
• commonly encountered bases
• alkylation of alkyne carbanions
• dialkylation
• limitation: only applies to methyl & 1º
Main topics include:
• Substitution/Elimination review
• alkynes: nomenclature
• structure of alkynes, review
• bonding/hybridization, review
• terminal alkynes as acids
• commonly encountered bases
• alkylation of alkyne carbanions
• dialkylation
• limitation: only applies to methyl & 1º
Lecture 22: April 2, 2009
Main topics include:
• alkyne alkylation review
• retrosynthetic strategies: alkynes
• double dehydrohalogenation
• hydrogenation of alkynes
• Lindlar Pd
• metal-ammonia reduction
• Hg cat. hydration
• addition of halogens
• hydroboration/oxidation of alkynes
Main topics include:
• alkyne alkylation review
• retrosynthetic strategies: alkynes
• double dehydrohalogenation
• hydrogenation of alkynes
• Lindlar Pd
• metal-ammonia reduction
• Hg cat. hydration
• addition of halogens
• hydroboration/oxidation of alkynes
Lecture 23: April 7, 2009
Main topics include:
• conjugated ∏-systems
• the allyl group
• allylic carbocation and radicals
• allylic SN1: stabilization of carbocat.
• allylic SN2: steric hind. & MO model
• rate of allylic SN2
• allylic halogenation: mechanism
• allylic halogenation in synthesis
• NBS
Main topics include:
• conjugated ∏-systems
• the allyl group
• allylic carbocation and radicals
• allylic SN1: stabilization of carbocat.
• allylic SN2: steric hind. & MO model
• rate of allylic SN2
• allylic halogenation: mechanism
• allylic halogenation in synthesis
• NBS
Lecture 24: April 9, 2009
Main topics include:
• classificiation/nomenclature of dienes
• delocalization energy
• conform. analysis (s-Cis, s-Trans)
• allenes & chirality
• prep. of dienes (elimination rxns)
• addition of HX to conjugated dienes
• thermodynamic/kinetic control
• Diels-Alder, stereospecificity
• Diels-Alder, activating groups
Main topics include:
• classificiation/nomenclature of dienes
• delocalization energy
• conform. analysis (s-Cis, s-Trans)
• allenes & chirality
• prep. of dienes (elimination rxns)
• addition of HX to conjugated dienes
• thermodynamic/kinetic control
• Diels-Alder, stereospecificity
• Diels-Alder, activating groups
Lecture 25: April 14, 2009
Main topics include:
• FMO theory applied to Diels-Alder
• drawing MO diagrams
• electronic effects on HOMO/LUMO
• symmetry-allowed cycloadditions
• regioselectivity of Diels-Alder
• sterespecificity of Diels-Alder
• Endo selectivity for EWGs
• Out-Endo-Cis rule
• Quiz 12 topics
Main topics include:
• FMO theory applied to Diels-Alder
• drawing MO diagrams
• electronic effects on HOMO/LUMO
• symmetry-allowed cycloadditions
• regioselectivity of Diels-Alder
• sterespecificity of Diels-Alder
• Endo selectivity for EWGs
• Out-Endo-Cis rule
• Quiz 12 topics
Lecture 26: April 16, 2009
Main topics include:
• Arenes & aromaticity
• Kekule formulation of benzene
• resonance energy
• π-MOs of benzene vs. 1,3,5-hexatriene
• net bonding in MOs; aromatic
• antiaromatic cyclobutadiene
• nomenclature
Main topics include:
• Arenes & aromaticity
• Kekule formulation of benzene
• resonance energy
• π-MOs of benzene vs. 1,3,5-hexatriene
• net bonding in MOs; aromatic
• antiaromatic cyclobutadiene
• nomenclature
Lecture 27: April 21, 2009
Main topics include:
• aromatic effects on structure & reactivity (e.g. acidity)
• Hükel's Rule: aromatic, antiaromatic
• Frost Circles
• Heterocylic aromatic compounds
• benzylic free radical halogenation
• benzylic SN1 & SN2 (MOs)
• preparation of alkenylbenzenes
• regioselectivity AdE to alkenylbenznes
Main topics include:
• aromatic effects on structure & reactivity (e.g. acidity)
• Hükel's Rule: aromatic, antiaromatic
• Frost Circles
• Heterocylic aromatic compounds
• benzylic free radical halogenation
• benzylic SN1 & SN2 (MOs)
• preparation of alkenylbenzenes
• regioselectivity AdE to alkenylbenznes
Lecture 28: April 23, 2009
Main topics include:
• Review: Electrophilic addition (AdE) to alkenes
• arenium ions
• electrophilic aromatic substitution
• nitration, sulfonation, bromination
• Friedel-Crafts alkylation
• Friedel-Crafts acylation
• rearrangement of 1º/2º chlorides
• Clemmensen & Wolf-Kishner [R]
Main topics include:
• Review: Electrophilic addition (AdE) to alkenes
• arenium ions
• electrophilic aromatic substitution
• nitration, sulfonation, bromination
• Friedel-Crafts alkylation
• Friedel-Crafts acylation
• rearrangement of 1º/2º chlorides
• Clemmensen & Wolf-Kishner [R]
Lecture 29: April 28, 2009
Main topics include:
• SEAr i>Clicker review
• Rate of SEAr: Effect of EDGs & EWGs
• Regioselectivity of SEAr
• Ortho/Para directors
• Meta directors
• Aromaticity video (Courtesy of Dr. Bob Widing)
Main topics include:
• SEAr i>Clicker review
• Rate of SEAr: Effect of EDGs & EWGs
• Regioselectivity of SEAr
• Ortho/Para directors
• Meta directors
• Aromaticity video (Courtesy of Dr. Bob Widing)
Lecture 30: April 30, 2009
Main topics include:
• nitrosonium ions
• strongly activating substituents: groups with electron pairs
• classification of activating effects
• degree of electron donations
• multiple substituent effects
• SEAr in synthesis: order matters!
• final exam info
Main topics include:
• nitrosonium ions
• strongly activating substituents: groups with electron pairs
• classification of activating effects
• degree of electron donations
• multiple substituent effects
• SEAr in synthesis: order matters!
• final exam info