CHEM 3332 1st EditionExam # 1 Study Guide Lectures: 1 - 8Test Material:FIRST EXAM: FRIDAY, FEBRUARY 20 at 7:00 PMWHERE: By first letters of LAST nameAH Aud 1: A – Pa of PM classAH Aud 2: Pe – Z of PM class and A – Ca of AM classSW 101: Ce – L of AM classSW 102: M – Re of AM classSEC 101: Ri – Z of AM classCOVERS: Org. I Review - Chapter 15I. Nomenclature 12 points all points are approximateII. Facts 16 pointsIII. Reactions 36 pointsIV. Mechanism 12 pointsV. Synthesis 12 pointsVI. Spectroscopy 12 pointsIMPORTANT DETAILS:• You MUST bring your picture ID (Cougar card) to the exam room.• You may use molecular models, but you must leave the directions to thekit at home.• You MAY NOT use or bring calculators, pagers, cell phones, or anyother electronic devices. No headphones, iPods, or wireless cell phoneearpieces.• You MAY NOT use scratch paper other than that provided with theexam.• You MAY NOT leave the room until you are finished with the exam.• You MAY NOT finish the exam and then stand (or sit) in the foyer.SEATING: Observing these rules will allow the exam to begin on time.• Begin filling rows with the aisle seats.• Leave TWO empty seats between each person. (Count from end of row.)• Sit directly behind the person in front of you. (eclipsed conformation)• Use the desk top of your seat, not an adjacent seatLecture 1: A Brief Review of Important Organic I ConceptsI. Lewis Structure/Formal Charge:Write an acceptable Lewis Structure for CO3. Indicate any formal charges.II. ResonanceCircle the more stable resonance contributorIII. Stability of intermediates:Rank the following carbocation’s of increasing stability (1 = least stable, 4 = most stable.) Rank the carbanions in order of increasing stability (1 = least stable, 4 = most stable.)A Brief Review of Organic I – Reactions and MechanismsI. AdditionsII. EliminationsIII. SubstitutionsIV. Rearrangements I. Additions: (alkane example, X more EN than Y)Mechanism Tips and Reminders- Identify nucleophile (Nu) and electrophile (E+)- Electron flow is always from electron rich (Nu) to electron poor (E+); never the reverse- Arrow always drawn from a lone pair of bond to a positive or δ+ atom - Mechanism arrows do not show where atoms “go”- In the presence of strong acids or strong electrophiles, do not form strong bases or strongNucleophiles- In the presence of strong bases or strong nucleophiles, do not form strong acids or strong electrophilesLecture 2:Alkene Oxidations: (addition of oxygen)A. Epoxidation with peroxyacidsAcid – catalyzed ring opening of epoxidesB. HydroxylationC. Oxidative CleavageAddition Mechanisms Continued: Additions of Alkynes A. Additions of H – X: similar to address to alkenes – intermediate is more stable C+ (Mark’s Rule)B. Addition of X2: 3-membered ring intermediate probably too strained; forms more stable C+ addition of first eq. X2 gives cis and trans productsC. Addition of H2: 3 choices 1. Gives alkane with H2 and active catalyst (Pt,Pd,Ni)2. Gives cis-alkene with H2 and Pd/Baso4/quinoline (Lindlar’s catalyst)3. Gives trans-alkene with Na or Li in liquid ammoniaD. Addition of H-OH: Does not give alcohols!1. Mark addition2. Non-Mark additionOxidation of alkynes:1. Mild:2. Strong:II/III. Elimination/Substitution Reactions:For Pathway A, E+ is δ+ Carbon = substitutionFor Pathway B, E+ is δ+ Hydrogen = emilinationSN1/E1: reactivity: 3 > 2 >1 >>> CH3 Step 1:Step 2:SN2:E2:Pathway that has the fastest rxn rate (lowest Ea/lowest E TS) forms major product – anticoplanarLecture 3:Substitution vs. Elimination (Wade summaries: sections 6-16 and 6-22)Exception: 1 halide with a strong, unhindered base – SN2 gives major productExamples:1.2.3.4.5.Synthesis of Alcohols HEAT R – X + -OH → R – O – H OR R – X + H – OH → R – O – HI. From Alkyl HalidesII. From Alkenes: Ch. 8A. Hydration (H3O+) = Mark/Inversion/RetentionB. Oxymercuration/ Demercuration: 1. Hg(OAC)2/H2O 2. NaBH4 = Mark /Anti additionC. Hydroboration: 1. BH3THF 2. H2O2/OH- = Non-Mark/Syn additionD. Epoxidation followed by an acidic hydrolysis: 1. MCPBA 2. H3O+ or CH3CO3H/H3O+ = Trans vicinal diolE. Hydroxylation: OsO4/H2O2 or cold, basic KMnO4 = Syn vicinal diolIII.From Acetylide Anion and Carbonyl Compound: Ch.9IV. Organometallic Reagents + Carbonyl Compounds (aldehyde/keytone/esters) → R-OH: Ch.10A. Preparation of ReagentsB. Mechanism of Grignard Reaction (mechanism of organolithium reaction is similar)1. With aldehydes and ketones:2. With esters or acid halidesV. Reduction of CarbonylsA. Hydride ReductionsReducing AgentsNaBH4: the milder choice: usually chosen for aldehydes and keytones- May use H2O or alcohol as solvents- Very slow reduction or esters; will not reduce acid chlorides or carboxylic acidsLiAlH4: more reactive than NaBH4- Reduced aldehydes, ketones, esters, acid halides and carboxylic acids- CAUTION: reacts violently with H2O and alcohols! Must use esters as solvents1. Reduction of aldehydes and keytones:2. Reduction of esters, acid halides and carboxylic acidsB. Catalytic Hydrogenation of Aldehydes and Ketones:- Catalytic reduction of carbonyl is slower than reduction of carbon-carbon double bond- Raney Ni is best catalystLecture 4:Reactions of Alcohols I. OxidationsA. Oxidation of 1 alcohols: B. Oxidation of 2 alcohols: C. Oxidation of 3 alcohols [ox] : 1. Chromic acid reagenta) Na2Cr2O7/H2SO4/H2Ob) CrO3/H2SO4/H2O/acetone/ 0 (Jones reagent) 2. Pyridinum chlorochromate / CH2CL2 (written as: PCC/CH2CL2 or CrO3 pyridine HCL/CH2CL2)II. Formation of the tosylate ester (converting the OH group to a better leaving group)III. Conversion of alcohols to alkyl halides – The BEST methodsA. Formation of 3 alcohols: use hydrohalic acids (HBR,HCL) B. Formation of 1 / 2 alkyl halides from 1 / 2 alcohols: 1. Bromides: use PBR32. Chloridesa) PCL3 or PCL5b) SOCL2 – NOTE: The mechanism given on Pg 463 occurs only in solvents like dioxane. The more typical mechanism is SN2 IV. Dehydration of alcohols to alkenes (first discussed in Ch.7)A. For 3 , 2 alcohols use H2SO4 (conc)/heat (Be careful!E1, so may rearrange)B. For 1 (and 3 , 2 that may rearrange) use POCL3/pyridine – E2, so no carbons NOTE: this reagent is given by Wade in a chapter problemV. Formation of EthersWilliamson Ether Synthesis (symm. Or unsymmetrical ethers)Lecture 5:VI. Ester FormationA. Fischer Esterfication (intermolecular dehydration) – mechanism this