RXNS: For each chemical reaction listed below it is anticipated that a student will be able to recall

• the reagents necessary to accomplish the transformation,
• the reaction stereochemistry, and
• the reaction regiochemistry.

The student should be able to apply this knowledge to

• predict the product of a specific reaction,
• suggest a suitable reactant to yield a specific product, and
• utilize the reaction in a synthetic scheme.

* Students should be able to provide a detailed mechanism for the chemical reactions marked with *.

Chapter 1-8:

Objectives

• RXNS:
  • Acid/Base Reactions* (including the deprotonation of terminal alkynes)
  • Nucleophilic Substitutions*
  • The following alkene and alkyne addition reactions:
  • • hydrohalogenation*
    • hydration*
    • halogenation*
    • oxymercuration*-reduction
    • hydroboration*-oxidation
    • hydrogenation
  • The following alkene addition reactions:
    • alcohol addition*
    • halohydrin formation*
    • epoxidation*
  • The following reactions of alkynes:
  • • hydrogenation with Lindlar's catalyst
    • conversion to trans-alkenes*
  • Diels-Alder Reactions*
• Know the language and grammar of Organic Chemistry.
  • Draw organic molecules with appropriate electrons and charges.
  • Name organic molecules.
  • Classify organic molecules by functional group.
  • Represent and recognize three-dimensional shapes on paper.
  • Classify any two molecules as being: identical or different, constitutional isomers or stereoisomers, enantiomers or diastereomers.
  • Represent reactions and reaction mechanisms using the appropriate arrow formalisms.
• Analyze the stability of organic molecules using bond strengths, electronegativities, resonance theory, molecular orbital theory, and analysis of electronic and steric interactions.
• Evaluate molecular reactivity.
  • Predict products based on reactants (and vice versa).
  • Use molecular orbital theory, resonance theory, and reaction coordinate diagrams, and mechanisms to understand reactivity patterns.
• Apply the mechanism of reactivity to compose a reaction coordinate diagram, predict reaction selectivity, and explain new results
• Compose the synthesis of an organic molecule by using the retrosynthetic method, assembling learned reactions, and evaluating multiple pathways

Spectroscopy: UV-visible and Infrared

Objectives

• Recognize the connections between MO diagrams, UV-vis absorption, color, and molecular structure
• Use the Beer-Lambert law to connect concentration and absorption
• Recall and apply the connection between wavelength, frequency, and energy
• Connect the IR absorption to a molecular vibration
• Explain the relative intensities of IR absorptions
• Explain why some vibrations are IR-active and others are IR-inactive
• Explain the frequency based on the bond strength, atomic masses, hydrogen bonding, resonance, and inductive effects
• Use the presence or absence of IR bands to identify the presence/absence of the following groups: (sp) ≡C-H, (sp²) =C-H, (sp³) C-H, O-H, N-H, -C≡C-, -C≡N, C=O, C=C

Skill-building Problems: in-chapter + UV: 44, 59; IR: 42, 43, 48, 49, 51, 56, 57, 61, 62

Quiz-like Problems: UV: 46, 64, 70; IR: 45, 54, 58, 60, 63, 65, 66

Chapter 9: Elimination Reactions

Objectives

• Be able to draw E1 and E2 reaction mechanisms
• Understand the factors influential in determining the mechanism of reaction: E1, E2, or other
• Recognize the regioselectivity of elimination reactions (Zaitzev's Rule)
• Recognize the stereochemical ramifications of the E2 mechanism
• Suggest conditions that favor either substitution or elimination over the other
• Use substitution and elimination reactions in syntheses

Skill-building Problems: in-chapter + 31-34, 36, 38-43, 46, 57

Quiz-like Problems: 35, 37, 44, 45, 47, 49, 51, 53-55

Spectroscopy: ¹³C-NMR

Objectives

• Predict the number of CNMR signals for any molecule.
• Recognize the role of symmetry and rotation in reducing the number of signals observed.
• Use the chemical shifts to determine the environment of each carbon.
• Use the splitting to determine the number of Hs attached to each C.
• Use a CNMR spectrum to identify an organic compound.

Skill-building Problems: in-chapter + 43b

Quiz-like Problems: 52, 53, 59, 64cd, 73

Chapter 10: Reactions of Alcohols, Amines, Ethers, Epoxides, and S Compds; Organometallic Compds

Objectives

• RXNS:
• • conversion of alcohols to alkyl halides w/ HX*, PX₃ or SOCl₂
  • conversion of alcohols to sulfonate esters
  • reaction of sulfonate esters*
  • dehydrations of alcohols*
  • oxidation of alcohols
  • nucleophilic substitution of ethers*
  • acid catalyzed* and base promoted* reactions of epoxides
  • reactions of thiols, sulfides, and sulfonium salts
  • formation of organometallic compounds (organolithium, Grignard reagents, Gilman reagents)
  • coupling reactions (Heck, Stille, Suzuki)
• Name thiols, thiolates, and sulfides.

Skill-building Problems: in-chapter + 44, 46, 48, 50, 54, 56, 57, 59, 60, 63, 64, 68, 70, 72, 75, 77, 79

Quiz-like Problems: 43, 45, 47, 49, 51, 52, 55, 58, 61, 62bd, 66, 67, 69, 73

Spectroscopy: ¹H-NMR

Objectives

• Predict the number of HNMR signals for any molecule.
• Use the chemical shifts to determine the environment of each H.
• Use integration to determine the number of equivalent Hs represented by each signal.
• Use the splitting to determine the connectivity of the molecular fragments.
• Use the J-coupling constants to identify geminal coupling, long-range coupling, and to distinguish between cis and trans double bonds.
• Use deuterium exchange to determine which protons are attached to O or N.
• Use a HNMR spectrum to identify an organic compound.

Skill-building Problems: in-chapter + 43a, 44, 48, 49, 57, 60, 61, 63, 65, 67

Quiz-like Problems: 45-47, 50, 51, 54, 58, 62, 64ab, 66, 69, 70, 74

Chapter 11: Radical Reactions

Objectives

• RXNS:
  • Anti-Markovnikov addition of HBr* to alkenes (and alkynes)
  • Alkane radical substitution reactions* with Br₂ and Cl₂.
  • Allylic and benzylic radical substution with NBS*
• Know the relative stability of radicals.
• Be able to represent radical mechanisms, recognizing the initiation, propogation, and termination steps.
• Apply the relative stability of radicals, probability, Bond Dissociation Enthalpies (BDEs), and mechanisms to rationalize the outcome of radical reactions.
• Recognize the applicability of Hammond's postulate to explain the higher selectivity found for radical bromination compared to radical chlorination.

Skill-building Problems: in-chapter + 20-26, 28, 31, 35, 36, 40

Quiz-like Problems: 29, 30, 32, 38, 39

Mass Spectrometry (MS) and Combined Spectroscopic Determination

Objectives

• Identify the the molecular ion peak (M) and use it to determine possible formulas.
• Use the "odd nitrogen rule" to determine if the molecule contains an odd number of nitrogen atoms.
• Recognize that all peaks lower than M come from fragmentation of the molecular ion with the most prevalent fragment representing the base peak (100 intensity).
• Recognize that the generally small peaks higher than M are due to heavier isotopes.
• Use the relative abundance of the M+1 peak to determine the approximate number of carbon atoms.
• Use the relative abundance of the M+2 peak to determine the presence of Cl, Br, or S.
• Be able to deduce the structure of a molecule efficiently by using spectroscopic information, MS, and/or chemical reactivity.

Skill-building Problems: in-chapter + MS: 41, 47, 67; Combo: 13.55

Quiz-like Problems: MS: 50, 52, 53; Combo: 12.69, 13.56, 13.71, 13.72

Chapter 14: Aromaticity and the Reactions of Benzene

Objectives

• RXNS:
  • Electrophilic Aromatic Substitution
    • Halogenation*
    • Nitration*
    • Sulfonation/desulfonation*
    • Friedel-Crafts alkylation* and acylation*
    • Gatterman-Koch reaction
  • Alkylation with Gillman, Stille, Suzuki reactions
  • Functional group changing reactions
    • Wolff-Kishner reduction
    • Clemmensen reduction
    • H2 reduction of phenyl ketones
    • NBS*
    • Interconversions of -NH₂ and -NO₂
    • oxidation to benzoic acid
• Recognize the reactivity difference between alkenes and aromatic double bonds.
• Recognize the MO explanation for the extra stability of aromatic systems and the consequences of that stability.
• Be able to identify molecules as aromatic, non-aromatic, or anti-aromatic.
• Be able to draw the pi MO diagram of any conjugated molecule with proper phasing, energetics, and filling.
• Be able to name the aromatic compounds on pp. 646, 651, and 652.

Skill-building Problems: in-chapter + 30, 33, 34, 35b, 36, 46, 49

Quiz-like Problems: 31, 32, 37-45

Chapter 15: Reactions of Substituted Benzenes

Objectives

• RXNS:
  • Creation and reactions of arene diazonium ions
  • nucleophilic aromatic substitution reactions
  • reactions involving benzyne
• Name compounds using ortho-, meta-, and para-
• Use IUPAC nomenclature to name compounds and draw structures.
• Recall the effects of various substituents on the rate of reaction (activating or deactivating) and on substitution position (o/p-directing or m-directing)
• Explain the effects mentioned above by drawing mechanisms and resonance structures.
• Design syntheses of polysubstituted benzenes.

Skill-building Problems: in-chapter + 39-41, 43, 44, 46, 48, 50, 51, 59, 60, 63, 64, 66

Quiz-like Problems: 34-36, 38, 42, 45, 47, 49, 52, 54-58, 57, 58, 61, 62, 65, 68

Chapter 16: Nucleophilic Acyl Substitution of Carbonyl Compounds

Objectives

• RXNS:
  • reduction of aldehydes and ketones by Grignard reagents and hydrides.
  • nucleophilic acyl substitution*
  • acid catalyzed hydrolysis and esterification of amides*
  • dehydration of amides to nitriles
  • Gabriel synthesis
  • hydrolysis of nitriles*
  • activation of carboxylic acids to acid halides (SOCl₂, PCl₃, PBr₃) or acid anhydrides (P₂O₅)
• Use the reaction conditions (acidic or basic) to propose a reasonable mechanism.
• Learn the redox reactions of alcohols, ketones, aldehydes, and carboxylic acids.
• Recognize the three loci of reactivity on a carbonyl compound.
• Differentiate between the reactions of carbonyl compounds and know their relative reactivities:
  • Ketones and Aldehydes have no potential leaving group.
  • Amides have poor leaving groups.
  • Acid halides, Acid anhydrides have good leaving groups.

Skill-building Problems: in-chapter + 48, 50, 51, 58, 66, 71, 72, 75, 78, 83, 85, 88

Quiz-like Problems: 45-47, 49, 52-57, 59, 60, 62-65, 70, 74, 77, 79-81, 84, 86, 87