Organic Chemistry I Lesson Objectives, Lesson Problems, Course Outline Spring 2008

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1 Organic Chemistry I Lesson Objectives, Lesson Problems, Course Outline Spring 2008 Lesson Date Assignment Lesson Objective Description Lesson Problems 4 14-Jan Chapter 1 Quiz Describe how bond polarity is attributable to electronegativity. Ch 2: 1, 2, 4, 6, 7, 8 Ch 2: 1-7 Differentiate among symmetrical covalent bonds, polar covalent bonds, and ionic bonds. Identify dipole moments, if any, in a molecule. Calculate the formal charge of an atom in a molecule Jan Ch 2: 9, 10, 14, 15 Draw resonance structures using electron-pushing arrows, and identify the most Ch 2: 9, 10, 11, 12 stable (lowest energy) structure. 13 Identify the Bronsted-Lowry or Lewis acid/base, and the conjugate base/acid in a Understand K a, pk a, and given pk a values, predict relative acid strength and acid-base reactivity in a 6 18-Jan Ch 2: 16, 18 Identify types of organic acids and recognize typical organic bases. Ch 2: 16, 17,18 Identify Lewis acids/bases, and using electron-pushing arrows, draw the reaction between a Lewis acid and a Lewis base. Describe noncovalent interactions (dipole-dipole forces, dispersion, hydrogen bonding Chapter 2 review questions: 19, 20, 26, 30b,c,f, 32, 33a,b,e, 36, 37, 39, 44a, 49, 51, Jan Chapter 2 Quiz Recognize and identify functional groups in an organic molecule and know the groups Ch 3: 1-4, 6-9 shown in Table 3.1 Given a molecular formula, draw constitutional isomers of alkanes and alkenes Identify a specific carbon atom in an alkane as 1, 2, 3 or Jan Ch 3: 11, 12 Name and draw the structure of a straight-chain or branched alkane. Ch 3: 10, 14 Name the alkyl group derived from a straight or branched alkane, consisting of up to four carbon atoms. Describe trends in boiling and melting points of alkanes in terms of intermolecular attractive forces Jan Ch3: 15, 17 Draw sawhorse representation and a Newman projection of staggered, eclipsed, Ch 3: 16, 18 anti, and gauche conformations of a given molecule. Distinguish between torsional and steric strain, and describe sources of each. Given energy cost data from Table 3.5, draw Newman projections for rotation about a carbon-carbon bond and then graph the potential energy vs. rotation, showing energy maxima and minima in the curve. Chapter 3 review questions: 21, 22, 24, 28, 32, 33c, 37a,c,d, 38, 40, 42, 44 1

2 10 30-Jan Exam #1 Chapters Feb Ch4: 1a,b, 2, 4, Write the name and draw structures for cycloalkanes Ch 4: 1c-f, 3, 7, 9 5, 8 Identify cis-trans isomerism in cycloalkanes Describe ring strain, what evidence there is for it, and its impact on the reactivity of a cyclic molecule. Define and distinguish between angle, torsional and steric strain. Draw Newman projections of conformations of cycloalkanes (with particular emphasis on cyclohexane) 12 4-Feb Ch4: 12, 14, 15 Identify axial and equatorial positions in the chair conformation of cyclohexane, before and after ring-flip. Ch 4: 13, 16, 17 Identify and calculate 1,3-diaxial interactions (Table 4.1) in monosubstituted cyclohexanes; identify the low and high energy conformations. Identify and calculate 1,3-diaxial interactions (Table 4.1) in disubstituted cyclohexanes; identify the low and high energy conformations. Identify and describe cis and trans conformations in polycyclic molecules. Chapter 4 review questions: 22, 24, 26, 30, 34, 36, 40, Feb Chapter 4 Quiz Identify and describe the four general types of organic reactions and the two general types of mechanisms. Ch 5: 1-7 Distinguish between heterolytic and homolytic bond cleavage. Describe and draw, using curved arrow notation, the three steps of a radical chain Describe the two step process and write the mechanism (using curved arrows) of H 2 O addition to ethylene. Identify the nucleophile and electrophile in each step Feb Ch 5: 8, 10, 11 Describe and draw, using curved arrows, the movement of electrons between a nucleophile and an electrophile to form a covalent bond in a reaction mechanism. Ch 5: 9 Understand the relationship between a balanced chemical equation, equilibrium constant (K eq ) and the standard free energy change (ΔG ). Based on the value of K eq, predict if a reaction is exothermic or endothermic Describe what the reaction rate (kinetics) and reaction equilibrium reveal about the Feb Ch 5: 12 Draw a reaction energy diagram, showing activation energy, location of reactant, transition state, intermediate, product, heat of reaction, energy axis and reaction Ch 5: 13 progress axis. Identify from a reaction energy diagram if a reaction is fast or slow, exo or endothermic, and single or multi-step. Compare and contrast laboratory reactions with biological reactions. Chapter 5 review questions: 14-16, 18, 20, 24, 28, 30, 34, 36, 38, 40 Ch 6: 1, 2, 3, 4a,e, 5a,d, 6 Write the names and provide structures for alkenes and alkynes, including common 8, 11c,d Feb Chapter 5 Quiz Calculate the degrees of unsaturation in a molecule. 2

3 names given in Table 6.1. Identify and describe cis/trans isomerism in alkenes Feb Ch 6: 14a, 15, 17 Describe and explain trends in relative stability of substituted alkenes. Write the mechanism, draw the reaction energy diagram, and predict the products for electrophilic addition of HX to an alkene. State, explain and predict reaction products based on Markovnikov s rule. Explain carbocation structure and trends in relative stability of different carbocations. Use and apply Can-Ingold-Prelog rules to determine E-Z designation and name to a Ch 6: 12, 14b,c,16, highly substituted alkene Feb Ch 6: 50 Explain and apply the Hammond postulate, and draw energy diagrams to illustrate the postulate. Ch 6: 19, 20 Write the mechanism for the reaction between HX and an alkene that results in a carbocation rearrangement. Chapter 6 review questions: 24, 27, 31a-c, 32, 42, 45, 46, 51, 52, 54, Feb Exam #2 Chapters Feb Ch 7: 1, 2 Write the elimination reactions of dehydrohalogenation and dehydration used to prepare alkenes. Ch 7: 3-6 Write the mechanism, draw the energy diagram, and predict the products for the: a. electrophilic addition of X 2 to an alkene b. electrophilic addition of H 2 and water to an alkene (making a halohydrin) c. acid-catalyzed hydration of an alkene. Write the mechanism, draw the energy diagram, and predict the products for the: a. oxymercuration / demercuration of an alkene to give the Markovnikov alcohol. b. hydroboration / oxidation of an alkene to give the non-markovnikov alcohol product. Draw the structures and illustrate the reaction geometry for an alkene hydroboration reaction, and explain why the product is non-markovnikov Feb Ch 7: 9 Write the reactions for the catalytic reduction (hydrogenation) of alkenes. Ch 7: 10, 11 Write the mechanism for the oxidation of alkenes via: a. epoxidation b. hydroxylation Synthesize simple alcohols Feb Ch 7: 12 Write the steps of radical additions to alkenes, using electron-pushing arrows. Ch 7: 13, 14, 15 Predict the products of electrophilic addition reactions of conjugated dienes, and explain why certain products are favored using the concept of the allylic carbocation Feb Ch 7: Describe the structure and hybridization of an alkyne. Ch 7: 16 Write the reaction for the preparation of an alkyne from a vicinal dihalide or a vinylic halide. Write the mechanism, draw the energy diagram, and predict the products for the: a. addition of HX to an alkyne. b. addition of stoichiometric quantities of X 2 to an alkyne, and excess X 2 to an alkyne. 3

4 c. addition of H 2 to an alkyne with Lindlar catalyst and Pd/C catalyst. Given an alkane, alkene and alkyne, rate them in order of increasing acidity and explain the trend. Know and apply Chapter 7 Summary of Reactions. Chapter 7 review questions: 7, 8, 18, 23, 24, 25, 30, 34, 36, 40, 41, Mar Ch 7 Quiz Name aromatic compounds and draw their structures. Ch 8: 1-4, 6 Explain the stability of aromatic compounds using the resonance description and the molecular orbital description. Explain and apply the Huckel 4n+2 rule Mar Ch 8: 6, 8, 9, 12 Describe the π electron structure of pyridine, pyrimidine, pyrrole and imidazole, and account for the aromaticity of a heterocycle. Ch 8: 10, 13, 14 Write the mechanism for the electrophilic aromatic substitution (EAS) reactions: a. aromatic halogenation. b. aromatic nitration. c. aromatic sulfonation. d. aromatic hydroxylation. Write the mechanism for: a. Friedel-Crafts alkylation. b. Fridel-Crafts acylation. Describe the limitations of Friedel-Crafts reactions. Predict and explain the products of Friedel-Crafts reactions involving carbocation rearrangements Mar Ch 8: 15, 16a, Describe and explain substituent effects in EAS reactions. Understand the different types of groups and their effects. Know rank order of groups shown in Figure Ch 8: 16b-c, 18, Describe activating and deactivating effects using electron donation and withdrawl. Explain orienting effects of ortho/para and meta directors in EAS reactions Mar Ch 8: 21a Write reactions for oxidation and reduction or aromatic compounds. Ch 8: 19, 21c-d, 22 Given a target molecule to synthesize, use retrosynthetic analysis to assemble a sequence of reactions to produce it. Know and apply Chapter 8 Summary of Reactions. Chapter 8 review questions: 28, 29, 30, 32, 34, 37, 40, 41, 47, 52, 59, 61, Mar Ch8 Quiz Identify and explain chirality and enantiomers. Ch 9: 1, 2, 3, 7, 8, 9 Describe the phenomenon of optical activity and techniques for quantifying optical rotation Assign R and S configuration to chiral centers Mar Ch 9: 13, 14 Identify and explain diastereomers and meso compounds. Ch 9: 12, 15, 20 Describe racemic mixtures and predict the chirality of a reaction product. Understand and apply the concept of isomers as outlined in Figure Mar Ch 9: 22 Explain the stereochemistry of reactions by writing the mechanisms of: Ch 9: 21, 23, 24, 25 4

5 a. Additon of H 2 O to an achiral alkene. b. Addition of H 2 O to a chiral alkene. Explain chirality at N, P, and S. Explain prochirality and apply it to biological chemistry. Describe examples of different isomers resulting in different activity in nature. Chapter 9 review questions: 31, 32, 43, 45, 47, 49, 52, 53, 57, 69, Mar Exam #3 Chapters Mar Ch 10: 1-3 Name and draw the structure of alkyl halides. Ch 10: 1-5 Review the preparation of alkyl halides (Sections 6.6 and 7.2) Describe the reactivity of 1 o, 2 o, 3 o alcohols to reaction with HX. Write reactions of alkyl halides with Grignard Reagents Mar Ch 10: 4-6 Describe the nucleophilic substitution reactions of the Walden s cycle. Ch 10: 6-12 Write the mechanism, explain the kinetics, and draw the energy diagram of the S N 2 Explain and apply the characteristics of the S N 2 reaction and how variables affect the reaction: a. steric effects. b. the nucleophile. c. the leaving group. d. the solvent Apr Ch 10: 7-11 Write the mechanism, explain the kinetics, and draw the energy diagram of the S N 1 Explain and apply the characteristics of the S N 1 reaction and how variables affect the reaction: a. the substrate. b. the leaving group. c. the nucleophile. d. the solvent. Explain and apply Zaitsev s rule. Write the mechanism for E2 elimination reactions Apr Ch 10: Write the mechanism for E1 and E1cB elimination reactions. Ch 10: 24 Describe biological elimination reactions. Know and apply Chapter 10 Summary of Reactions Chapter 10 review questions: 28, 30, 31, 32, 33a-c, 34, 35, 37c-d, 38, 39, 43a, 44a-b, 49, 51, 52, Apr Chapter 10 Quiz 37 9-Apr Ch 11: 5-8 Describe magnetic-sector mass spectrometry instruments used to analyze small molecules. Use mass spectrometry to identify common functional groups and simple molecules. Explain the electromagnetic (EM) spectrum in the context of Figure and radiation s affect on molecules and atoms. Ch 10: 13, 15, 16, 17, 19, 20, 21 Ch 11: 1-4 Ch 11: 5, 6c-e, 7, 8, 9, 10 5

6 Understand and apply the quantitative relationships between Planck s constant (h), wavelength (λ), frequency (ν), energy (ε), and wavenumber (cm -1 ). Explain the conditions required for absorption of IR radiation. Interpret IR spectra using fingerprint (Figure 11.14) and functional group regions (Table 11.1) Apr Ch 11: Explain the conditions required for absorption of UV radiation. Ch 11: 11, 12, 13 Interpret UV spectra qualitatively and quantitatively (absorbance, concentration, path length, molar absorptivity, lambda max). Understand the effect of conjugation on UV absorption and apply it to the chemistry of vision. Chapter 11 review questions: 23, 25, 26, 27, 29b-c, 30a, 31, 32b-d, 37, 41, 45, Apr Ch 11 Quiz Qualitatively describe NMR spectrometry, NMR absorptions, chemical shifts (Figure 12.5), 13 C signal averaging and FT-NMR, and 13 C characteristics. Ch 12: 2,3, 5-10 Describe DEPT 13 C NMR. Use 13 C NMR for structure determination. Qualitatively describe 1 H NMR spectroscopy and proton equivalence Apr Ch 12: 13, 15 Correlate 1 H chemical shift with chemical environment (Table 12.3). Ch 12: 14, 16 Integrate 1 H NMR absorptions to count protons Apr Ch 12: 17 Interpret spin-spin splitting patterns and peak heights in 1 H NMR to determine nearby proton environment. Ch 12: 18, 19, 20 Assign a chemical structure from a 1 H NMR spectrum. Qualitatively describe more complex spin-spin splitting patterns using a tree diagram Apr Ch 12: Integrate MS, IR, UV, 13 C NMR, and 1 H NMR techniques to determine chemical structure. Ch 12: 21, 22 Chapter 12 review questions: 30, 31, 35, 40, 43, 46, 48, 50, 52, 53, Apr Exam #4 Chapters