Page 1 of 5 CHEMISTRY 231 FALL 2014 List of Topics / Examination Schedule Unit Starts Topic of Study 20 Aug 2014 STRUCTURE AND BONDING Suggested Reading: Chapter 1 29 Aug 2014 ALKANES & CYCLOALKANES Suggested Reading: Chapter 2, Appendix 9 10 Sep 2014 STEREOCHEMISTRY AND CHIRALITY Suggested Reading: Chapter 3, Appendix 8 17 Sep 2014 ACIDS AND BASES Suggested Reading: Chapter 4, Appendix 2 29 Sep 2014 ALKENES Suggested Reading: Chapters 5 & 6 13 Oct 2014 ALKYNES Suggested Reading: Chapter 7 27 Oct 2014 ALKYL HALIDES & RADICAL REACTIONS Suggested Reading: Chapter 8, Appendices 1 & 3 03 Nov 2014 NUCLEOPHILIC SUBSTITUTION/ELIMINATION Suggested Reading: Chapter 9 17 Nov 2014 ALCOHOLS Suggested Reading: Chapters 10 14 Sep 2014 EXAMINATION #1 (Friday) covering Chapters 1 3, Appendices 8 9 24 Oct 2014 EXAMINATION #2 (Friday) covering Chapters 1 7, Appendices 2, 8 9 03 Dec 2014 EXAMINATION #3 (Wednesday) covering Chapters 1 9, Appendices 1 3, 8 9 Student learning in this course is currently assessed with hand-written homework assignments, in-class assessments (quizzes) based on these same homework assignments, and three cumulative in-class examinations. At the end of the semester students are expected to pass a cumulative final exam covering, in part, all topics covered by the course of study indicated (see reverse).
Page 2 of 5 Sketch the 1s, 2s and 2p atomic orbitals (with mathematical shading) and write the electronic configuration for all elements in the first three rows of the periodic chart. Show in a sketch how the sp 3, sp 2 and sp hybrid orbitals may be constructed from the simple atomic orbitals. Explain the bond angle for the hydrides of all the elements through F using both the VSEPR and orbital hybridization models. Deduce molecular formula from composition and molecular weight. Calculate the formal charge on an atom in a small molecule. Predict the direction and relative magnitudes of the dipole moments of simple molecules. Describe the molecular events occurring during melting and boiling for ionic and covalent compounds and molecular crystals like diamond. Predict the relative solubilities, melting points, boiling points and relative acidities and basicities of simple compounds and explain your choice with reference to structure. Explain by words and equations the factors affecting the rate of a chemical reaction. Identify the major functional groups and the types of reactions they undergo. Name by the IUPAC system any saturated hydrocarbon whose parent chain contains 10 or fewer carbon atoms and no more than two simple rings (or sketch the hydrocarbon given its IUPAC name). Sketch the conformations of ethane, propane, butane, cyclopropane, cyclobutane, cyclopentane, and cyclohexane and simple substituted compounds derived from them. Describe (graphically and verbally) the relation between conformation and potential energy for ethane, propane and butane and closely related compounds (Newman projections). Describe (graphically and verbally) the relation between conformation and potential energy for cyclohexane. Calculate the relative energies of disubstituted (e.g. methyl) cyclohexanes, assuming chair conformations and using the relative energies of monosubstituted cyclohexane or butane. Define and recognize stereoisomer, enantiomer, diastereomer, conformation, configuration, meso, epimer, resolution. Given their structures, state whether 2 compounds are enantiomers or diastereomers or some other kind of isomer. Predict the number of stereoisomers of a compound of known bonding. Sketch a molecule with a chiral center so as to show unambiguously the configuration using both Fisher projection and perspective drawing.
Page 3 of 5 Determine the configuration (R or S) of any chiral center from a Fischer projection, perspective drawing, cyclohexane framework or molecular model. NOTE: prerequisite: recognize chirality. Predict from the structure whether a pair of stereoisomers can be interconverted by a conformational change and thus might not be separable. Calculate specific rotation from the experimental rotation and concentration. Define and recognize inversion, retention and racemization. Draw conclusions about the mechanism of a reaction from the stereochemistry. Given a proposed mechanism for a reaction, predict the stereochemistry. Define and recognize regioselective, stereoselective and stereospecific reactions. Describe a common method of resolution of a racemic modification. Name any alkyl halide whose parent chain is 10 carbons or less by the IUPAC system and sketch an alkyl halide given its IUPAC name or alkyl name. Given energy data (or relative rate data) and other experimental information about a reaction, sketch a graph of energy vs. reaction progress. Explain the difference between a transition state and an intermediate. Use the existing experimental evidence to describe the basis of our current understanding of the mechanisms of nucleophilic substitution at sp 3 carbon. Write chemical equations to outline the mechanism for a particular halide. Use nucleophilic substitution in a synthetic plan of several steps, taking into consideration elimination, rearrangement and stereochemistry. Note that some of these reactions form carbon-carbon bonds. Predict the products, including stereochemistry, of a nucleophilic substitution of an alkyl halide. Predict (and explain) the effect of alkyl, vinyl and aryl substituents on nucleophilic substitution. Given the identity of nucleophile, leaving group, substrate and solvent, predict whether elimination or substitution will predominate for a particular alkyl halide substrate. Outline in chemical equations the mechanisms of elimination of alkyl halides. Describe the experimental information collected about this reaction and how the mechanisms are deduced from this information. Define and use correctly the terms S N 2, S N 1, E2, E1. Draw conclusions about the mechanism of a reaction from the stereochemistry. Given a proposed mechanism for a reaction, predict the stereochemistry. Given the predominant diastereomer in a stereoselective or stereospecific reaction, provide a mechanistic explanation for the preference.
Page 4 of 5 Describe the evidence for the existence of carbocations and their relative stabilities. Predict and recognize simple carbocation rearrangements (H, CH 3 ). Name any alcohol whose parent carbon chain consists of 10 or fewer atoms by the IUPAC system and sketch the alcohol given its IUPAC name or carbinol name. Predict the relative acidity of alcohols by referring to the stability of all species in the equilibrium. Using our current understanding of the mechanisms of the two addition reactions, explain why simple acid- catalyzed addition of water can give a different product in both stereochemistry and orientation from the hydroboration-oxidation. Note that the oxymercuration [Hg(OAc) 2 ] / reduction is more regioselective than simple acid-catalyzed addition of water. Show how the mechanism of the hydroboration reaction is deduced from the experimental data about the reaction. Write chemical equations to describe the mechanism, showing transition states if necessary. Outline the synthesis of an alcohol from an alkene, an alkyne, alkyl halide, an epoxide, or an ether. Outline the currently accepted mechanisms of the substitution of an alcohol by halogen using haloacids and describe the experimental evidence for the mechanism. Use haloacids, thionyl chloride, and/or the phosphorus halides for the conversion of an alcohol to an alkyl halide in a synthetic route. Give the IUPAC name of any ether with 12 carbons or fewer in its parent chain and sketch an ether given its IUPAC name or alkyl name. Write the currently accepted mechanism for the Williamson Ether Synthesis Write the currently accepted mechanism for the hydrolysis of ethers. Outline a synthetic plan using the preparation of an epoxide from an alkene. Outline a synthesis using the conversion of an epoxide to an alcohol, halohydrin or ether-alcohol. Outline a stereospecific synthesis of a cis or trans 1,2-diol from an alkene. Write the currently accepted mechanism of the base-catalyzed and acidcatalyzed cleavage of epoxides Given sufficient structural detail, identify a particular alcohol or ether using the C- I-P and IUPAC conventions Identify uses of alcohols, diols, polyols, epoxides, ethers and polyethers. Sketch the molecular orbitals (bonding and antibonding) for ethene and their relative energies. Name by the IUPAC system any alkene or alkyne whose parent chain contains 10 or fewer carbon atoms and sketch the alkene given its IUPAC name.
Page 5 of 5 Define, recognize and name alkene diastereomers (Z/E, cis/trans); predict the direction of the difference in their physical properties and chemical stability. Define, recognize and name alkyne positional isomers; predict the direction of the difference in their physical properties and chemical stability. Outline the synthesis of a given alkene from an alkyl halide, alcohol, alkyne, or alkane (including stereochemistry). Outline the synthesis of a given alkyne from an alkyl halide, alcohol, alkene, or alkane (including stereochemistry). Write chemical equations to describe the currently accepted mechanism(s) of dehydrohalogenation of an alkyl halide (including stereochemistry). Explain how this mechanism is deduced from the experimental data. Write chemical equations to describe the currently accepted mechanism(s) of dehydration of an alcohol (including stereochemistry). Explain how this mechanism is deduced from the experimental data. Describe the evidence for the existence of carbocations and their relative stabilities. Predict and recognize simple carbocation rearrangements (H, CH 3 ). Predict the alkenes formed by elimination reactions of given starting materials. Predict the alkynes formed by elimination reactions of given starting materials. Predict the products or use in a synthetic plan the following reactions of alkenes (including stereochemistry): addition of halogen, addition of hydrogen halide, addition of water, oxymercuration, addition of carbocations (polymerization and alkylation), addition of hydrogen, and hydroboration. Predict the products or use in a synthetic plan the following reactions of alkynes (including stereochemistry): addition of halogen, addition of hydrogen halide, addition of water, oxymercuration, addition of carbocations (polymerization and alkylation), addition of hydrogen, and hydroboration. Write chemical equations to describe the currently accepted mechanism of addition of halogens to both alkenes and alkynes (including stereochemistry). Explain how the mechanism is deduced from the experimental data. Write chemical equations to describe our current understanding of the mechanism of addition of acids (HX, H 3 O +, H 2 SO 4 ) to both alkenes and alkynes. Explain how the mechanism is deduced from the experimental data. Using a reasonable mechanism for the reaction, explain why the orientation of addition of HBr is sometimes "anti-markovnikov" and what experimental evidence exists for the explanation. Write the mechanism for the acid-catalyzed addition of an alkene to itself.