|
|
|
|
CHEM 3750 Lecture Keywords |
|
| Lecture Notes - updated 11/16/09, 3 PM | |
| I will regularly post keywords for each lecture. |
|
| Syllabus and Schedule | |
| Syllabus pdf available here | |
| Schedule pdf here | |
| Ch 1 Molecular Bonding and Geometry, HW # 1-21, 24, 25, 26, 28, 36, 38, 48, 52, 55, 56 | |
| Ch 2 Alkanes and Cycloalkanes, HW # 1-17, 20, 22, 26, 27, 34, 39, 44, 48, 49, 51 | |
| Ch 3 Stereochemistry, HW # 1-10, 14-18, 20, 26, 27, 30, 31 | |
| Ch 4 Acids and Bases, HW # 1-10, 14-17, 26, 32, 33, 36, 37 | |
| Ch 5 Alkenes, HW # 1-10, 13, 14-16, 20, 31, 32, 35 | |
| Ch 6 Reactions of Alkenes, HW # 1-10, 13-17, 20-22, 25-28, 34-39, 41, 44, 47 | |
| Ch 7 Alkynes, HW # 1-12, 17, 20, 23, 27 | |
| Ch 8 Halides HW # 1-10, 13, 18, 22-24, 28 | |
| Ch 9 Substitution and Elimination Reactions, HW # 1-13, 17-20, 22, 25-28, 34, 37-40, 43, 46-47 | |
| Ch 10 Alcohols, HW # 1-16, 19-21, 25-28, 29, 31, 35, 37 | |
| Ch 15 Organometallic Compounds, HW # 1-7, 10-13, 17 | |
| Ch 11 Ethers, HW # 1-12, 15-17, 20, 21, 24, 27, 32, 33, 40 | |
Please note that leftover handouts will be available from the white desk outside my office in 3148 Wood Hall. |
|
| W 9/9/09 | |
| Introduction, discussion of course syllabus, information sheet for SI instructions | |
| F 9/11/09 Ch 1 Covalent Bonding and Shapes of Molecules |
|
began clicker registration. Discussed electronic structure, configuration, valency, energies of s and p orbitals, Lewis dot structures, electronegativity, polarity, bonding, charges, partial charges (delta), arrows (move TWO electrons), half-hook arrow (move ONE electron), octet rule, functional groups (FGs): alkanes |
|
| M 9/14/09 Ch 1- clicker registration continued | |
| common bonding patterns (i.e. H is monovalent, C is tetravalent, also see N and O), Lewis structures, formal charges, octet rule, classification, polar and nonpolar molecules, VSEPR, functional groups (RH for alkanes, ROH for alcohol, RCHO for aldehyde, R2CO for ketones; also see carboxylic acid / ester / amide) | |
| W 9/16/09 - Ch1, clicker registration continued | |
| reviewed formal charges, Molecular Orbital (MO) theory, carbon configuration and its hybridization, s-, p-, sp-, sp2-, sp3-orbitals, sigma and pi bonds, single / double / triple bonds, bonding and antibonding orbitals (productive and destructive orbital overlap), energy levels of orbitals, node (nodal plane), correlation between hyrbidization and geometry (tetrahedral, trigonal, linear), resonance structures (resonance arrow), use of arrows (move two electrons with curved arrow, move one electron with half-hook arrow), move only electrons in resonance structures (never move atoms) | |
| F 9/18/09 - Ch 2 Alkanes and Cycloalkanes, clicker registration continued | |
| reviewed resonance structures and hybridization, began Ch 2: hydrocarbons; saturation and unsaturation, unsaturation via multiple bonds (double, triple); formulae for alkanes, alkenes, alkynes, ie alkane has CnH2n+2. Structural drawings: line-angle formula versus structural fromula and molecular formula; constitutional isomerism (same molecular formular but different connections), IUPAC nomenclature, R-groups as subsituents on parent chain | |
| M 9/21/09 - Ch 2, official clicker points begin, ensure that you are registered | |
| IUPAC nomenclature, R-groups as subsituents on parent chain, multiple substituents, common R-groups (Me, Et, Pr, i-Pr, Bu, i-Bu, s-Bu, t-Bu). Common names of alkanes (isopropane, isobutane); classification of carbon and hydrogen; importance of suffix; cyclohexanes (CnH2n) like cyclopropane, cyclohexane, cycloheptane, cyclooctane; bicycloalkanes like decalin and norbornene, bridgehead; conformation of alkanes, Newman projections of ethane (staggered and eclipsed), correlation to stability (energy) | |
| W 9/23/09 - Ch 2 | |
| conformational isomers (conformers) of ethane and butane; drawing of Newman projections; strain energy from torsional / angle / steric strain; eclipsed and staggered conformations; gauche and anti conformations of butane; 1,2-dichloroethane; strain in cyclopropane / cyclobutane / cyclopentane; chair and boat conformations of cyclohexane and how to draw them; axial and equatorial bonds in the chair conformation of cyclohexane; chair ring flip; interconversion of equatorial and axial positions | |
| F 9/25/09 - Ch 2 (Handout: Exam 1 Practice Questions) | |
| Review of Newman projections; cyclohexane ringflip (two possible chair conformations); methylcyclohexane - comparison of equatorial and axial methyl position; 1,3-diaxial (axial-axial) interaction makes chair conformers with axial substituents less stable; Table 2.4 with Gibbs free energy value when certain groups are in equatorial (preferred) position; isomerism - constitutional versus stereoisomers - cis/trans isomers as stereoisomers (substituents: cis=same sides; trans=opposite sides), examples (which conformer is favored?): trans-1-tert-butyl-4-methylcylcohexane; cis-1,2-dimethylcyclopentane; trans-1,2-dimethylcyclopentane; cis-1,2-dimethylcylcohexane, trans-1,2-dimethylcylcohexane; stereocenters; converting planar hexagons into chair conformations (also see HW 2.13 and 2.14 as well as 2.48 and 2.49); fused rings (cis and trans decalin, also see steroids) | |
| M 9/28/09 - Ch 2 | |
| conformations of substituted cyclohexanes, interconversion of hexagon drawing to chair drawing; physical properties of alkanes; dispersion forces, how they behave in branched and unbranched alkanes and their effects on boiling points and stability, heat of combustion, | |
| W 9/30//09 - Exam 1 (Ch 1, 2) | |
| F 10/2/09 - Ch 3 Stereochemistry, returned Exam 1 | |
| chirality (handedness), chiral and achiral molecules, image and mirror image = enantiomers, superimposable and nonsuperimposable structures (examples: 2-butanol, cis-cyclohexan-1,3-ol, trans-cyclohexan-1,3-ol, plane of symmetry in structues, stereocenters (mostly carbon with 4 different substituents), R/S-system and assignment of priorities (CIP-rule) | |
| M 10/5/09 - Ch 3 | |
| R/S convention, phantom atoms (vinyl vs isopropyl), assigning R or S configuration (2-chlorobutane), Fischer projections, enantiomers and diastereomers, erythrose and threose and their enantiomeric and diastereomeric relationships | |
| W 10/7/09 - Ch 3 | |
| Fischer projections and allowable manipulations; R/S configurations, enantiomeric and diastereomeric relationships; properties of enantiomers and diastereomers (see three tartaric acid stereoisomers), meso compounds; plane-polarized light, specific rotation, [a]D values, levorotatory / dextrorotatory, optical activity; chirality and enzymes. | |
| F 10/9/09 - Ch 4 Acids and Bases, 2-page Handout | |
| Ch3: racemic mixture, resolution, Ch4: definitions of acids and bases (Arrhenius, Bronsted-Lowry), protons, hydronium ions; proton donor / proton acceptor, use of curved arrows; conjugate acid / conjugate base, resonance, formal charges (IMPORTANT! see pp 13/14), pi-electrons as basic sites, reactions of 2-butene with proton; formation of secondary carbocations | |
| M 10/12/09 - Ch 4 | |
| acid dissociation constants and pKa-values; equilibria for HA; correlation of pKa and acid strength (see Table 4.1); comparison of acidity of acetic acid and ethanol; acid base equilibria and pKa values (equilibrium to the right or left); relative strength of acids and bases; molecular structure and acidity: a) electronegativity, b) size of atom, c) resonance delocalization, d) electron-withdrawing inductive effect, e) hybridization. How aspects a) to e) affect the stability of A- and in turn the acidity of H-A. | |
| W 10/14/09 - Ch 5 | |
| alkene properties, general formulae and degrees of unsaturation (idex of hydrogen deficiency) for alkanes / alkenes / alkynes / arenes; reviewed sigma and pi bonds and the preferred geometries; cis / trans isomerism; calculating index of hydrogen deficiency (IHD, NOTE: mistake in textbook on p. 185, for group V elements like nitrogen - subtract (not add) one hydrogen from formula; IUPAC and common names of alkenes; special substituents (methylene, vinyl, allyl); cis / trans system; E / Z system | |
| F 10 /16/ 09 - Ch 5, 2 handouts (alkene nomenclature) | |
| IUPAC and common names of alkenes; special substituents (methylene, vinyl, allyl); cis / trans system; E / Z system; cycloalkenes; dienes / trienes / polyenes, properties of alkenes, practice questions | |
| M 10/19/09 | |
| Exam 2 (Ch 3,4,5) | |
| W 10/21/09 - Ch 6, 1 handout (classification) | |
| energy diagrams, reaction coordinate, Gibbs free energy change (exergonic, endergonic), enthalpy change, heat of reaction (exothermic, endothermic), activation energy, transition state, one- versus two-step reactions, alkene additions (e.g. hydrohalogenation and hydration), use of Lewis acids / Lewis bases and electrophiles / nucleophiles in mechanisms; mechanism of addition of HX to alkenes, regioselectivity (orientation), Markovnikov's rule, carbocation stability; RETURNED EXAM 2 | |
| F 10/23/09 - Ch 6 | |
| Addition of HX and H2Oto alkenes, Markovnikov's rule, carbocation stability (hyperconjugation), +CH3 is least stable, +C(CH3)3 (tertiary) is most stable; hydration reaction; general mechanism for addition reactions across double bonds (first add electrophile, then add nucleophile); carbocation rearrangement (a hydrogen or an alkyl group on the adjacent carbon migrates to the carbocation WITH its bonding electrons, ultimately changing to a more stable carbocation) | |
| M 10/26/09 - Ch 6 | |
| addition of HX (hydrohalogenation); H2O (hydration); X2 (halogenation); X2+H2O (halohydrin formation); anti-stereoselectivity for addition of X2 and X2/H2O, and for reactions with mercury acetate, oxymercuration-reduction (=hydration with Markovnikov regioselectivity), use of NaBH4 as hydride source to remove mercury | |
| W 10/28/09 - Ch 6, 2 handouts | |
| hydroboration-oxidation (hydration with non-Markovnikov regioselectivity); oxidations (loss of electrons, increased number of C-O bonds, decrease of C-H bonds); reductions (gain of electrons, decrease of C-O bonds, increase of C-H bonds); oxidation with OsO4 to yield syn diol; ozonolysis; reduction of alkenes in the presence of a catalyst; stability of alkenes. | |
| F 10/30/09 - Ch 7 Alkynes | |
| Alkynes: nomenclature; common names of alkynes (as derivatives of acetylene); hybridization and geometry; acidity of alkynes (pKa 25) and use of sodium amide (NaNH2), sodium hydride (NaH) and lithium diisopropylamide (LDA); deprotonation of alkyne with NaNH2, NaH or LDA; preparation of alkynes: a) alkylation of acetylide anion with alkyl halide (methyl or primary best, elimination with secondary or tertiary halides) | |
| M 11/2/09 - Ch 7, 1 handout (hydration of alkynes) | |
| deprotonation of alkyne with NaNH2, NaH or LDA; preparation of alkynes: a) alkylation of acetylide anion with alkyl halide; b) dehydrohalogenation from alkenes (1. Br2; 2. NaNH2); reactions of alkynes: electrophilic addition (X2 or HX, look for similarities to alkenes); regioselectivity of different hydration methods: hydration of alkynes with mercury (HgSO4, H2SO4, H2O) yields methyl (or alkyl) ketone; hydration with 1)Sia2BH and 2) H2O2, NaOH yields aldehyde; keto-enol isomerism; reductions of alkynes: H2 in the presence of a catalyst yields alkane (reduces triple and double bonds, but not the double bonds in an aromatic ring), H2 in the presence of Lindlar's catalyst affords syn addition of H2 and STOPS (!) at the cis-alkene, the "dissolving metal reduction" (Na, NH3-liquid) yields the trans alkene (anti reduction); | |
| W 11/4/09 - Ch 8 Haloalkanes, Halogenation, Radical Reactions | |
| Focus on a) radical halogenation, b) allylic halogenation, c) radical addition of H-X to alkenes; nomenclature (IUPAC and common, especially see alkyl, vinyl, allyl and aryl halides); properties of halides (boiling point, polarizability, bond strength); stability of radicals; regioselectivity of bromination and chlorination | |
| F 11/6/09 - Ch 8 | |
| regioselectivity of bromination and chlorination (Hammond postulate); mechanism for radical chain reaction (initiation, propagation, termination); allylic hydrogens and mechanism for subsitution in allylic halogenation; mechanism of HX addition to alkenes: a) no peroxides, ionic mechanism, Markovnikov product, b) with peroxides, radical mechanism, non-Markovnikov product | |
| M 11/9/09 Exam 3 (Ch 6, 7, 8) ----------- Last day to withdraw from course ------------- | |
| W 11/11/09 - Ch 9, Substitution and Elimination Reactions, returned Exam 3 | |
| nucleophilic substitution reactions and elimination reactions; 3 mechanisms: SN1, SN2, E1, E2; use of abbreviations: electrophile (E+), nucleophile (Nu-), leaving group (lv), SN2 reaction mechanism | |
| F 11/13/09, 6-page handout | |
| Examples of nucleophilic substitution reactions; SN2 mechanism: one-step transformation with transition state (ST), simultaneous bond formation and bond breaking, backside attack, inversion of configuration, rate= bimolecular; SN1 mechanism: achiral carbocation as intermediate after the fist step; two transition states, racemic mixture (mixture of R and S); effect of carbocation stability on kinetics, effect of solvents (polar, nonpolar, protic, aprotic) | |
| M 11/16/09 | |
| review of SN1 and SN2 reactions, solvent effects; trends in nucleophilicity; rearrangements (hydrogen and methyl shift); E1 mechanism (begins with solvolysis like SN1); competition of SN1 and E1; Zaitsev's rule and alkene stabilty | |
| W 11/18/09 | |
| competition of SN1 and E1; Zaitsev's rule and alkene stabilty; E2 mechanism (regio-and stereoselectivity), co-planar anti groups in Newman projection for elimination | |
| F 11/20/09 | |
| structure and properties of alcohols, nomenclature, comparison of structural features and effect on boiling points and solubility; reactions of alcohols (with metal or sodium hydride- formation of alkoxides) | |