Handouts, Spring 2007-8

Lecture-related material

• Course syllabus (PDF)
• Laboratory manual (1MB PDF)
• Organic acids and bases
• 1/9/2008: Organic qualitative analysis, points of unsaturation and getting from a molecular mass to a formula. Mass spectrometry.
  • Powerpoint
• 1/11/2007: Infrared spectroscopy and Fourier transforms.
  • Powerpoint
• 1/16/2007: Introduction to NMR spectroscopy
  • Powerpoint
• 1/18/2007: Splitting patterns and integration in NMR
  • powerpoint
• 1/23/2008: C-13 NMR including DEPT
  • C-13 NMR
  • C-13 practice problems and answers
• 1/25/2008:Interpreting combined H-1 and C-13 data
• combined spectroscopy practice problems and answers
• 2/8/2008: Molecular orbital theory and Valence bond theory
  • Powerpoint
    • printable version
  • Quiz given in class today (answers on pagge 2)
• 2/11/2008: π molecular orbitals and the stability of benzene
  • bonding in benzene
  • how to construct π MOs for linear poly-enes
• 2/13/2008: UV/VIS spectroscopy and conjugation
  • powerpoint
• 2/15/2008: Conformation and strain, sections 2.10-2.14
  • Worksheet covering today's topics (don't look at the answers until you work the problems!)
  • Conformation and Newman Projections on the Molecular Models website
• 2/18/2008: Reaction rates and equilibria
  • powerpoint
• 2/20/2008: Reaction coordinate diagrams and how to think about reaction rates
  outline of material
• 2/22/2008: The Diels-Alder reaction
  • The important points covered in the chapter and lecture
  • Online molecular models and orbital diagrams illustrating the basic concepts
• 2/25/2008: Nucleophilic substitution reactions in more depth
  • Nucleophilic substitution
  • MO explanations of reactivity (covers some of the same material)
  • Reaction animations
    • S_N2
    • S_N1
• 2/27/2008: Elimination reactions in more depth
  • MO explanations of reactivity
  • Reaction animations
    • E2
    • E1
• 3/10/2008: Mechanisms of free-radical chain reactions
  • Powerpoint
• 3/12/2007: Synthetic utility of free-radical chain reactions
  • Powerpoint
  • In-class worksheet with #3 as a five-point quiz problem. Here are three possible answers to #3:
    
    
    (a) Br₂ (free-radical bromination); (b) potassium tert-butoxide (elimination); (c) BH₃, then NaOH, H₂O₂; (d) PCC or Swern oxidation; MnO₂ only works on benzylic alcohols
    
    
    (a) Br₂ (free-radical bromination); (b) potassium tert-butoxide (elimination); (c) HBr and peroxide; (d) NaOH (S_N2 reaction); (e) PCC or Swern oxidation
    
    
    (a) Cl2 (free-radical chlorination produces about 40% of 1-chlorobutane); (b) NaOH (S_N2 reaction); (c) PCC or Swern oxidation
• 3/14/2008: Organometallic couplings and a review of Carbonyl I reactions
  • Powerpoint with notes, reiterates Section 10.13
  • In-class worksheet includes two synthesis problems that are due Monday.
    • The first problem (4-cyclopent-1-enylanisole) is a Heck coupling reaction between cyclopentene and 4-methoxyphenyl triflate. You can make the two Heck ingredients from the starting materials.
    • The second problem (due Monday) is probably the most difficult. You will need to use two different organometallic coupling reactions, and probably something from Chapter 11.
    • In the second section, you should be able to put a mechanism together by careful study of Section 17.8.
    • The synthesis problem is an application of the reaction you just drew a mechanism for, between cyclohexanone and N-ethylethanamine. You can make cyclohexanone from cyclohexene in two steps.
    • The last reaction is more of an aromatic-substitution reaction, but also involves making an ester (Chapter 16).
• 3/17/2008: Synthons and disconnects; protecting groups and the Wittig reaction
  • Powerpoint
  • homework answers
• 3/19/2008: Problems with synthesis; introduction to α,β-unsaturated carbonyls
  • Powerpoint
• 3/26/2008: α,β-unsaturated carbonyl compounds; acidity of C-H bonds α to carbonyls and other EWGs (see the reading).
• 3/28/2008: Enols, enolates and enamines: substitution α to carbonyl groups; the Aldol reaction and E1_CB reactions (see your textbook)
  • Handout; we went over #1 in class and you handed in #2 as a quiz (answers are on page 2).
    • I was astonished that nobody realized that you can do S_N2 substitution just as well on ethyl as on methyl halides. Nobody recognized that the top ketone is better because there is no difference between the two sides: there can be no unwanted product as long as you can keep it from alkylating more than once.
  • 3/31/2007: Enolate nucleophiles, carbonyl electrophiles: The Michael, Stork, Aldol and Claisen reactions. Check the textbook for mechanisms.
    • Synthetic utility of these reactions (new bonds shown in red)
  • 4/4/2008: Review. NMR interpretation and predicting an ¹H NMR spectrum; reactions of carbonyl compounds.
    • outline of reactions
  • 4/7/2008: Cyclization and decarboxylation reactions: the Dieckmann cyclization; intramolecular Aldol; the Robinson annulation; the Malonic and Acetoacetic Ester syntheses
    choosing methods for synthesis
  • outline of reactions
  • 4/11/2008: Oxidation and reduction reactions
    • Is it oxidation or is it reduction?
  • 4/14/2008: Oxidation and reduction reactions
    • synthesis problem worked in class
  • 4/16/2008: exam 3 review
    • Problems worked in class
  • 4/18/2008: amine reactions
  • 4/21/2008: Synthesis of amines; reactions of heteroaromatic compounds
    • worksheet used in class
    • Heterocyclic compounds you should know
    • A discussion of Problem 20.30
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  Exam answers

  • CEM 221 exams, Fall 2007-2008
  • Exam, February 4 and answers
  • Midterm Exam (corrected -- there was a typo in the one you took) and answers (explains the typo)
  • Exam, April 9 and answers
  • Take-Home Final Exam and answers
    • The "answers" file contains literature references, from which you may obtain the answers. All journals referenced are available through the OhioLink Electronic Journal Center or as hard copies in Musselman library.

  Lab Data; see the lab schedule

  Data from group experiments will be posted here as PDF documents.

  Virtual Spectroscopy

  Individual assignment pages are posted here, by name:
  

  Balogun	Biru	Creque	Gordon	Irojah	Kadangs
  Leopold	Phillips	Pothast	Singian	Sweitzer

  Organic Qualitative Analysis

  Here is the student assignment list, which tells which unknowns are assigned to which student. Mass spectral data (and boiling points of liquids) are tabulated here.

  IR spectrum of Nujol

  Keto-enol equilibrium studies by NMR

  Raw integration numbers may be obtained from this Excel spreadsheet (right-click, then save).
  
  Assume that the enols of 2,4-pentanedione (acetylacetone), 1-phenyl-2,4-pentanedione (benzoylacetone) and ethyl 3-oxobutanoate (ethyl acetoacetate) have the structures shown below.

  

  Kinetics of the esterification of trifluoroacetic acid by NMR

  We will compare the rates of esterification of three of the four different C₄H₁₀O alcohols: 1-butanol, 2-butanol and 2-methyl-1-propanol.

  tert-Butyl alcohol reacts reversibly with trifluoroacetic acid, and so the rate constant is not trivial to obtain from NMR data.

  The raw data, with last year's values for comparison, are contained in this Excel spreadsheet. You will need to calculate the rate constants by taking the reciprocal of the experimental T1 values.
  
  You should account for differences in the rate constants in terms of structure. Be sure to explain whether you think the observed differences are significant. (Hint: statistical analysis will be needed to determine this.)
  
  

  Diels-Alder Reaction

  Spectra of the starting materials, simulated spectra of two possible products, and spectra of the actual product obtained. Report is due Thursday, March 20.
  spectral file (2 MB PDF)
  
  

  Alkyl halide results

  Results are posted here (Excel spreadsheet). The report is due Friday, March 28.