Test Topics

Unit 1, Test 1

• Intro, Electron Structure, Bonding -- Introductory material, atomic structure, electron configuration (standard notation - ground and excited), ionic bonding, covalent bonding (polar and non-polar), determining bond type (bring your electronegativity chart!), determining polarity, determining and drawing dipoles

• Representing Organic Molecules -- Drawing Lewis dot structures, determining formal charge and dot structure stability, other structures (condensed, Kekule', and skeletal)

• Molecular Orbital Theory and Orbital Hybridization -- General principles of molecular orbital theory, atomic and molecular orbitals, orbital hydridization, sigma and pi bonds, formation and structure of carbon-carbon bonds (single, double, and triple), bond lengths, bond strengths, bond angles (for sp, sp2, and sp3 hybridized atoms)

• Laboratory -- General questions over Lab #1 (recrystallization and melting point analysis).

Unit 1, Test 2 -- Test will be cumulative, though the focus will be on the below topics

• Resonance (electron delocalization) -- General principles of resonance, requirements for resonance (i.e. pi or lone pair electrons), identification of structures that exhibit resonance, drawing resonance contributors, predicting stability of resonance contributors (predicting which contributor the resonance hybrid most closely resembles), resonance energy (why resonance stabilizes compounds), identification of compounds with increased stability based on increased resonance energy, how resonance energy relates to the observed color of a compound

• Acids and Bases -- Bronsted-Lowry definition, what "strength" and "weakness"/"stability" mean in the context of acids and bases, conjugate acids/bases (what conjugates are, how they differ in strength), Ka and pKa and how these numbers change with acid strength (know the specific pKa values and associated compound classes from the table presented in lecture), definition of protonation and how this term applies to acids and bases (i.e. when a compound is protonated, it becomes more acidic), effect of compound structure on acid/base strength (electronegativity, atomic size, inductive electron withdrawal, resonance energy)

Unit 2 Test – Test will be cumulative, though the focus will be on the below topics

• Alkanes: Basics, Nomenclature, and Properties -- Definition of alkane molecule class, alkane nomenclature (including cycloalkanes and cis/trans geometric isomers of disubstituted cycloalkanes), alkyl group nomenclature, constitutional isomers, difference between primary, secondary, and tertiary carbons, physical properties of alkanes (boiling point, melting point, solubility) and associated trends, chemical properties of alkanes (acidity/reactivity of alkanes in relation to compound classes already studied, alkane solubility), presence of alkanes in nature as natural gas and oil (and why), fractional distillation and crude oil refining (see associated reading), definition of an alkane conformation/conformer.

• Acyclic Alkanes -- Drawing conformers of acyclic alkanes using Newman projections, definition of torsional strain, eclipsed vs. staggered conformers of acylic alkanes and associated stability (example = ethane), definition of steric strain, syn vs. gauche vs. anti conformer(s) of acyclic alkanes and associated stability (example = butane).

• Cyclic Alkanes -- Strain types affecting cyclic alkanes (torsional, steric, and angle strain), puckered conformers of cyclopentane and why they are the most stable, why 6-membered rings are the most common cyclics in nature (stability!), chair conformers of cyclohexane and why they are the most stable, drawing both chair conformers (ring flips) for a given mono- or di- substituted cyclohexane, axial vs. equatorial bonds, stability of chair conformers of monosubstituted cyclohexanes (i.e. determining which chair conformer, if either, is the more stable), definition of 1,3-diaxial interactions (in specific! - i.e. what is the significance of "1,3"?), definition of a geometric isomer, cis and trans geometric isomers of disubstituted cyclohexanes and how to recognize them, stability of cis vs. trans geometric isomers of disubstituted cyclohexanes (chair conformers), effect of substituent size on stability of chair conformers of mono- and di- substituted cyclohexanes.

• Connections with Biochemistry – Definition of a carbohydrate (saccharide), definition of a sugar, examples of saccharides (mono-, di-, and poly-), how deoxyribose sugar puckering affects the structure of DNA.

• Laboratory -- General questions over Lab #2 (simple distillation and gas chromatography)

Unit 3 Test -- Test will be cumulative, though the focus will be on the below topics

• Alkenes: Basics, Nomenclature, Physical Properties, Isomerism -- Definition of alkene molecule class, alkene nomenclature, saturated vs. unsaturated hydrocarbons, determining molecular formulas for saturated and unsaturated hydrocarbons, alkene geometric isomers, E/Z nomenclature of alkene geometric isomers, relative stabilities of alkyl-substituted (general) and 1,2-dialkyl substituted alkenes, impact of carbon hybridization on acidity (acidity of alkenes vs. alkanes).

• Alkene Reactions: General Principles – Why alkenes are more reactive than alkanes, functional groups (definition), alkene functional group (double bond), why functional groups react similarly, definition of nucleophile vs. electrophile

• Physical Chemistry Concepts -- Thermodynamics vs. kinetics, endergonic (+ΔG°) vs. exergonic (-ΔG°), activation energy, transition state vs. intermediate, rate-determining step, how stability of transition state relates to reaction rate

• Alkene Electrophilic Addition: General + Addition of Hydrogen Halide -- Reactivity of alkenes (principles behind electrophilic addition), reaction mechanism for electrophilic addition of hydrogen halide to alkene (nucleophile and electrophile at each step, how to draw arrows in mechanism), predict major product(s) for electrophilic addition of hydrogen halide to alkene, physical chemistry concepts as applied to electrophilic addition of hydrogen halide to alkene (e.g. transition state, intermediate, fast vs. slow steps, rate-determining step, exergonic reaction, endergonic rate-determining step, etc.)

• Alkene Electrophilic Addition: Carbocation Stability Specifics – How the concepts of inductive electron withdrawal, hyperconjugation, and resonance specifically relate to carbocation stability, ranking of tertiary vs. secondary vs. primary vs. methyl vs. benzyl vs. allyl carbocations in terms of stability, Hammond's postulate (and how it applies to exergonic vs. endergonic rate-determining steps), how stability of carbocation intermediate relates to stability of transition state in electrophilic addition reactions (and how this, in turn, relates to certain products being formed much faster than others), predict major product(s) for electrophilic addition of hydrogen halide to alkene when more than one product is possible, definition of regioselectivity, degrees of regioselectivity, ranking reactions in terms of degree of regioselectivity

• Carbocation Rearrangements -- Mechanism for 1,2-methyl shift, mechanism for 1,2-hydride shift, mechanism for 1,2-ring expansion shift, predicting when 1,2-methyl shifts/1,2-hydride/1,2-ring expansion shifts occur in reactions, determining which type of shift occurs (if any) in a given reaction, predicting major product(s) of reactions involving 1,2-methyl/1,2-hydride/1,2-ring expansion shifts

• Laboratory -- General questions over Lab #3 (extraction)

Fall Final Exam -- Test will be cumulative, and it will include the below additional topics

• Alkene Electrophilic Addition: Acid-Catalyzed Addition of Water -- Definition of hydration reaction, why/how (mechanistically) strong acids catalyze the addition of water to alkenes, mechanism for acid-catalyzed addition of water to an alkene, predicting the major product(s) of acid-catalyzed addition of water to an alkene

• Alkene Electrophilic Addition: Acid-Catalyzed Addition of Alcohol -- Why/how (mechanistically) strong acids catalyze the addition of alcohol to alkenes, mechanism for acid-catalyzed addition of alcohol to an alkene, predicting the major product(s) of acid-catalyzed addition of alcohol to an alkene

• Alkene Electrophilic Addition: Addition of Halogens -- Why/how a halogen serves as an electrophile in this reaction (alkene π bond induces dipole between halogens, etc.), use of dichloromethane as solvent in this reaction, reaction mechanism for addition of halogens to alkene, why reaction only occurs with Br2 and Cl2, why carbocation rearrangements do not take place in this reaction, predicting the major products(s) of addition of halogens to an alkene

• Alkene Electrophilic Addition: Addition of Hydrogen -- Definition of hydrogenation reaction, why group 10 metals are used to catalyze addition of hydrogen to alkene, basics of mechanism for hydrogen addition to alkene (see graphic on lecture slide), predicting the major product(s) of addition of hydrogen to an alkene

• Alkene Electrophilic Addition: Hydroboration-Oxidation -- Molecular formula of borane, why boron in borane is electrophilic, why borane is dissolved in THF for use in experimental chemistry, why boron adds to the LESS substituted carbon in electrophilic addition step, mechanism for electrophilic addition steps of hydroboration-oxidation (you need to know, mechanistically, how a tri-alkyl borane is formed from an alkene and borane/THF), predicting the major product(s) of hydroboration-oxidation of an alkene, molar ratios of reactants/products in hydroboration-oxidation (3 mol alkene + 1 mol BH3 yields 1 mol tri-alkyl borane, 1 mol tri-alkyl borane + H2O, OH-, and H2O2 yields 3 mol of alcohol), why no carbocation rearrangements take place in hydroboration-oxidation of alkene

• General -- Determine the reagents required to convert a given reactant to a given product, determine whether a given organic reaction is an oxidation, a reduction, or neither (Bruice Ch. 19, Problem 1).

• Nomenclature – Basic alcohol and ether nomenclature

Unit 4 Test -- Test will be cumulative, though the focus will be on the below topics

• Stereochemistry: Intro, Nomenclature, Enantiomers -- Definition of stereoisomer and how it differs from a constitutional isomer, different types of stereoisomers, definition of chirality, definition of asymmetric (chirality) center, definition of enantiomer, R/S nomenclature system, naming and drawing all stereoisomers for compounds with one asymmetric (chirality) center, how to distinguish enantiomers from identical molecules

• Stereochemistry: Diastereomers, Meso Isomers -- 2n rule for determining maximum number of potential stereoisomers, correctly naming and drawing all stereoisomers for compounds with more than one asymmetric (chirality) center, definition of diastereomer, how diastereomers differ from enantiomers, definition of meso isomer, how to recognize meso isomers, identifying asymmetric carbons in cyclic compounds

• Stereochemistry: Physical and Chemical Properties -- Physical and chemical properties of enantiomers, definition of polarized light, definition of optical activity, optical inactivity of racemic mixtures, physical and chemical properties of diastereomers, different ways to experimentally separate enantiomers

• Stereochemistry of Electrophilic Addition Reactions -- Definition of stereoselectivity, difference between regioselectivity and stereoselectivity, determination of when stereochemistry matters in reactions, stereochemistry of reactions that form carbocation intermediate (addition of hydrogen halides, acid-catalyzed addition of water, acid-catalyzed addition of alcohol), stereochemistry of reactions that DO NOT form carbocation intermediate (addition of hydrogen, hydroboration-oxidation, addition of halogens), determining stereochemical relationship between products of these reactions AND whether or not mixture of products is equal or unequal (based on whether or not reactant has asymmetric carbon(s)), definition of SYN addition, definition of ANTI addition, stereochemistry of electrophilic addition to cyclic alkenes. Review “Important Reminders” slide!

• Stereochemistry in Biochemistry -- Be able to list and describe multiple examples illustrating the importance of stereochemistry in biochemistry

• Laboratory -- General questions over Lab #5 (Column Chromatography and Spectrophotometry)

Unit 5 Test -- Test will be cumulative, though the focus will be on the below topics

• Dienes: Intro, Rxns of Isolated vs. Conjugated, Kinetic vs. Thermodynamic Control -- Three general classes of dienes, diene nomenclature, why conjugated dienes are more stable than isolated dienes, predicted product(s) of electrophilic addition to dienes (isolated or conjugated) using excess or limiting electrophilic reagent (for reactions WITH carbocation intermediates), difference between kinetic and thermodynamic products, explanation for why kinetic and thermodynamic products can be different, kinetic vs. thermodynamic reaction control and conditions required for each

• Dienes: Diels-Alder Reaction -- MECHANISM of reaction (including specifics -- concerted, pericyclic), basic explanation of reaction via molecular orbital theory, importance of electron-withdrawing groups, predicting major product(s) given reagents (using excess or limiting diene), predicting major product(s) both reactants are unsymmetrically substituted (using excess or limiting diene), stereochemistry of Diels-Alder reaction, predicting major product stereoisomer(s) (if applicable), s-cis vs. s-trans in terms of stability and ability to participate in Diels-Alder, predicting major product(s) of Diels-Alder reactions with ringed dienes locked in s-cis, endo vs. exo isomeric configurations of bridged bicyclic compounds, relative stabilities of endo vs. exo (especially in terms of predicting major products), naming of bridged bicyclic compounds (only for extra credit)

• Alkynes: Intro, Nomenclature Review, Physical Properties -- Definition of alkyne functional group, alkyne nomenclature, structure of alkynes (in terms of orbital hybridization, types of bonds involved, and geometry), determining molecular formulas of alkynes (given on number of carbons and degrees of unsaturation -- i.e. number of rings and/or pi bonds), physical properties of alkynes (noting especially how they differ from alkenes and alkanes in terms of physical properties), carbon hybridization vs. electronegativity trends, carbon hybridization vs. acidity/basicity, pKa's to know (see lecture slides for updated chart)

• Alkynes: Electrophilic Addition Reactions, Part 1 -- Why alkynes are less reactive than alkenes, despite being less stable (be able to explain in terms of potential energy associated with transition state of rate-determining step), predicting product(s) of electrophilic addition of hydrogen halides to alkynes in presence of limiting or excess electrophilic reagent, stereoselectivity of these reaction class (ANTI addition favored) and why, regioselectivity of this reaction class (halogens always add to the same carbon) and why, predicting product(s) of electrophilic addition of halogens to alkynes in presence of limiting or excess electrophilic reagent, stereoselectivity of this reaction class, when carbocation shifts can happen in the above reactions (and when they cannot!)

• Alkynes: Electrophilic Addition Reactions, Part 2 -- Predicting product(s) of acid-catalyzed addition of water to alkynes, use of mercuric ion catalyst in this reaction class, keto-enol tautomerization (associated definitions, MECHANISM of acid-catalyzed keto-enol tautomerization, ketone product favored in equilibrium), definition of carbonyl group, definition of ketone and aldehyde functional groups, predicting product(s) of hydroboration-oxidation of alkyne, rationale for use of disiamylborane (or other bulky borane), difference between aldehyde and ketone in terms of product formation, how to form ketone from terminal alkyne, how to form aldehyde from terminal alkyne, predicting product(s) of catalytic hydrogenation of alkyne, how to stop this reaction at the alkene stage (use of Lindlar catalyst), stereochemistry of catalytic hydrogenation with Lindlar (SYN addition), predicting products of reaction of alkyne with sodium or lithium in liquid ammonia (at -78 deg. C), stereochemistry of these reactions (ANTI addition), mechanistic rationale for ANTI addition in these reactions (radical anion formed in mechanism; E radical anion more stable than Z radical ion due to having less steric strain)

• Laboratory – General questions over Lab #6 (Catalytic Hydrogenation) and Trans-Fatty Acids + Margarine reading

Unit 6 Test -- Test will be cumulative, though the focus will be on the below topics

• Acetylide Substitution -- Mechanism of reaction (and concepts involved), required reagents, relevance to multi-step synthesis

• Multi-Step Synthesis -- Multi-step synthesis problems (best form of study is to complete practice problems -- complete and study the examples from the lecture slides, the in-class practice activity, and the homework), know the REAGENTS involved in all the reactions studied thus far (so that you can use them to complete multi-step synthesis problems), retrosynthetic analysis (know the relevance of this technique to multi-step synthesis and be able to apply it) 

• Lead Compounds and Molecular Modification – Be able to list and describe multiple examples

• Laboratory – General questions over Lab #7 (Diels-Alder Reaction)

Unit 7 Test -- Test will be cumulative, though the focus will be on the below topics

• Nomenclature -- Know how to name simple benzene derivatives.

• Spectroscopy (General) -- Definition of spectroscopy, properties of electromagnetic radiation and how they are related (energy, wavelength, frequency, wavenumber)

• Infrared Spectroscopy -- Different types of bond vibrations (stretch vs. bend), how IR spectroscopy works (concepts/principles involved), characteristic IR stretching AND bending vibrational absorption bands (bring your handout to the exam!), high energy vs. low energy on IR spectrum, location of function group region vs. fingerprint region on IR spectrum, typical types of vibrations in functional group region vs. fingerprint region, definition of band intensity and why bands have different intensities on an IR spectrum, influence of symmetry on IR activity (what type of compounds are infrared inactive?), know the different variables/factors that affect the position and broadness of an absorption band on an IR spectrum AND how/why they specifically do (IMPT!), review tips for analyzing IR spectra (IMPT!), know how to calculate degrees of saturation for compounds with C, H, O, N, S, or halogens, review practice IR spectra slides.

• 1H NMR Spectroscopy

1. • From Part I -- NMR background concepts, how 1H NMR works (concepts/principles involved), concept of diamagnetic shielding (and how it relates to 1H NMR signal position), predicting how many signals will be exhibited on the 1H NMR on a given compound (based on the number of chemically equivalent proton groups), importance of TMS to 1H NMR, definition of chemical shift, effect of electron withdrawal on chemical shift (and rationale behind this effect), characteristic values of 1H NMR chemical shifts (bring your handout to the exam!).

1. • From Part II -- Importance of integration of 1H NMR signals, using integral trace to determine relative number of protons contributing to signals in 1H NMR spectrum, concept of signal splitting (i.e. what are 1H NMR signals sometimes split?), N+1 rule and its usefulness in analyzing signal splitting, concept behind determining relative peak intensities in split signal, Pascal’s triangle mnemonic and its usefulness in explaining relative peak intensities in split signal, concept of long-range coupling, definition of coupling constant, factors affecting coupling constant, how coupling constants can be useful in evaluating 1H NMR spectra, approximate values of different coupling constants (bring your handout to the exam!), tips for analyzing 1H NMR spectra (located on summary slide –VERY IMPT!).

1. • From Part III -- Complex 1H NMR signal splitting (i.e. when/why this occurs), definition of multiplet and why all peaks in this splitting pattern are often not observed, effect of hydrogen bonding on chemical shift (for cases of protons bonded to O or N), proton exchange (know mechanism of acid-catalyzed proton exchange; be able to explain why OH and NH2 protons do not split signals of neighboring protons AND why OH and NH2 proton signals are not split by neighboring protons).

• Unknown Analysis via IR and 1H NMR -- Review steps for analysis of unknown when given molecular formula, IR spectrum, and 1H NMR spectrum (see review slide – VERY IMPT!), know how to calculate degrees of unsaturation for compounds containing C, H, O, N, S, or halogens, know how to determine the chemical structure of an unknown compound when given its molecular formula, its IR spectrum, and its 1H NMR spectrum (review in-class practice problems– VERY IMPT!).

• MRI (Magnetic Resonance Imaging) -- Know general concepts behind this medical technology (see lecture slide).