Organic Chemistry 220 Final Exam Preparatin D all hmewrk, WebAssign prblems, and wrksheets until yu n lnger have t lk at ntes, bks, r ther prblems t answer them crrectly. Wrk extra prblems t further cncretize any material if needed (ha! Are there any extra prblems left after all f the wrk I have given yu? ). This study guide is nly a rugh guide (this is my legal disclaimer ). Yu are respnsible fr all f the material that I have cvered in chapters 10, 11, 13, 14 (and all f the ld stuff t: chapters 1-9) and the class lecture ntes. The Final Exam will have: Nmenclature Shrt synthesis reactin (reactants t prducts) Mechanisms Multi-step synthesis Cnceptual questins Big cncepts t keep in mind: Yu need t knw all f the reagents required fr the reactins that are utlines belw. Yu need t knw the mechanisms that I have utlined belw. Knw all sterchemical utcmes f the reactins that we cvered. Yu need t be able t carry ut multi-step synthesis reactins. Sme Basics t Review Nmenclature pka stuff Resnance S N 1, S N 2, E1, E2 Sterechemistry Chapter 1 Lewis structures Electrnegativity Bnd plarities and diple mments Frmal charges Resnance; drawing structures and predicting which resnance is best Cndensed structural frmulas Line-angle frmulas Acids and bases Arrhenius acid/base Brnsted-Lwry acid/base Lewis acid/base Acid strength Predicting acid base reactins, d we favr reactants r prducts? (pka s) Structural effects f acidity Electrnegativity Size Resnance Chapter 2 s-rbital p-rbital Mlecular rbital thery (MO) Bnding and antibnding m s s-s verlap Jhn Cngletn, Orange Cast Cllege
s-p verlap p-p verlap (head n) pi-bnding Hybridizatin sp 3, sp 2, sp where are the unhybridized p-rbitals relative t the hybridized rbitals? Be able t draw rganic cmpunds shwing the rbital verlap (single, duble, triple bnds etc ) Ismers Be able t draw cnstitutinal ismers Cis/trans ismers Intermlecular frces LDF D-D H-bnding Predicting BP Predicting slubility Knw the functinal grups Chapter 3 Alkane nmenclature Names t structure Structure t names Cmplex substituents Cmmn names (isprpyl, etc ) Physical prperties f alkanes MP, BP f branched and straight chain alkanes Reactins Cmbustin Cracking Structure f alkanes Newman prjectins Ptential energy diagrams & Newman prjectins Ttally eclipsed Partially eclipsed Gauche Anti Dihedral angle Be able t draw Newman prjectins fr alkanes Cyclalkane nmenclature Stability f cyclalkanes Heats f cmbustin: what d they mean? Angle strain and trsinal strain Cyclhexane Chair and bat cnfrmatins Twist bat cnfrmatin Half-chair cnfrmatin Axial and equatrial psitins Be able t flip the chair (as in figure 3-23) Be able t draw and predict which chair structure is mre stable fr mnsubstituted cyclhexanes Be able t draw and predict which structure is mre stable fr disubstituted cyclhexanes Be able t draw and predict which chair structure is mre stable fr cyclhexanes with bulky substituents Nmenclature f bicyclic alkanes Jhn Cngletn, Orange Cast Cllege
Chapter 4 Free radical chain mechanism (all f the sterps) ΔG and equilibrium cnstants Enthalpy, entrpy, Gibbs BDE Magnitude f BDE and stability f free-radical Activatin energy Reactin energy diagrams Activatin energy Exthermic Endthermic Multistep reactins energy diagrams Hw des temperature influence reactin rates? Selectivity f chlrinatin Can yu determine the percents fr prducts Selectivity f brminatin Can yu determine the percents fr prducts Free-radical stability Hypercngjugatin and inductive effects Why is brminatin s much mre selective? Allylic brminatin What is the Hammnd Pstulate What des the transitin state have t d with this pstulate? Be able t determine chlrinatin and brminatin prducts taking sterechemistry int cnsideratin Chapter 5 Definitins: Chiral, achiral, enantimer, diasteremer, mes, R, S, plane f symmetry Be able t determine if a mlecule is chiral Be able t determine if a mlecules are enantimers, diasteremers, different mlecules, etc Determine R and S fr all types f mlecules Fischer prjectins Line structures Newman prjectins Be able t name cmpunds using R/S sterechemistry Draw Fischer prjectins frm line structures and vice-versa Optical activity What is it? Are racemic slutins ptically active? What des ± mean in frnt f a cmpund? Can yu determine R and S frm + and -? Chapter 6 Knw the detailed mechanisms fr: S N 1, S N 2, E2, and E1. Be able t predict prducts (including sterechemistry) f: S N 1 S N 2 E2 E1 Jhn Cngletn, Orange Cast Cllege
Be able t predict whether a reactin will prceed via S N 1 and E1 S N 2 S N 2 and E2 E2 What makes a gd nuclephile? What makes a gd base? What makes a gd leaving grup? What is meant by high and lw plarizability? Allylic brminatin Understand, be able t predict, and be able t cmplete mechanisms that invleve hydride and methyl shifts. During E1 and E2 reactins what will be the majr alkenes? Zaitsev s rule When d we use this? Hffman prduct (anti-zaitsev s rule) When are these prducts favred? The summary table n page 251 shuld be memrized The summary table n page 264 shuld be memrized Chapter 7, Alkenes Framewrk f the alkene Calculatin f elements f unsaturatin & drawing pssible ismers Nmenclature f alkenes (including E/Z) What are the stabilities f alkene? Bredt s rule Alkene synthesis Dehydrhalgenatatin, knw mechanism, sterechemistry, etc Bulky bases and Hffman prducts E2 reactins (anti-cplanar!, knw mechanism, sterechemistry, etc ) E1 reactins (knw mechanism, sterechemistry, etc ) Alkene synthesis via dehydratin reactins Knw this mechanism Chapter 8: What is an electrphile? What is a nuclephile? What is an anti-additin? What is a syn-additin? Additin f hydrgen halides t alkenes (8-3) Knw mechanism, sterechemistry, etc Knw Markavnikv s rule What are the prducts in the presence f perxides? Can it wrk will all hydrgen halides? Knw the mechanism, sterechemistry, etc (8-3b). Additin f water t alkenes (8-4) Acid-catalyzed hydratin Knw the mechanism, sterechemistry, etc Oxymercuratin-demurcuratin (8-5, 8-6) Knw the mechanism, sterechemistry, etc Hydrbratin (8-7) Knw the mechanism, sterechemistry, etc Dn t wrry abut the secnd step f the mechanism (page 340, H 2 O 2, NaOH) Additin f Halgens (8-10) Knw the mechanism, sterechemistry, etc Jhn Cngletn, Orange Cast Cllege
Can armatic duble bnds react? Frmatin f halhydrins (8-9) Knw the mechanism, sterechemistry, etc Catalytic hydrgenatin Knw the sterechemistry and the required types f catalysts Skip 8-11 Epxidatin (8-12) Knw the mechanism, sterechemistry, etc Skip 8-13 Syn Hydrxylatin (8-14) Knw the reagents and the sterechemistry f this reactin Oxidative cleavage (8-15) What is the difference between znlysis and adding warm KMnO 4? What prducts are frmed? Skip 8-16 Chapter 9: Nmenclature f alkynes Hw d yu name cmpunds with a duble bnd and a triple bnd? And an alchl? Structure f the triple bnd Acidity pf alkynes Synthesis f alkynes frm acetylides Knw the mechanism, sterechemistry, etc Knw the additins t ketnes and Aldehydes t Synthesis f alkynes via eliminatin What are the differences between the additin f: KOH, 200 C and 1) NaNH 2, 150 C, 2) H 2 O Additin reactins f alkynes Skip 9-10 Hydrgenatin Knw the difference when yu add: H 2 and Pt, Pd, r Ni Lindlar s catalyst Na, NH 3 (Knw the mechanism, sterechemistry, etc fr this ne) Skip 9-9D Skip 9-9E Hydratin f alkynes (9-9f) Knw the mechanism, sterechemistry, etc fr the additin f an alkyne with HgSO 4 / H 2 SO 4 Knw the mechanism, sterechemistry, etc f acid-catalyzed ket-enl tautmerism Knw the mechanism, sterechemistry, etc fr the additin f an alkyne with 1) SiaBH.THF 2) H 2 O 2, NaOH Knw the mechanism, sterechemistry, etc f base-catalyzed ket-enl tautmerism. Chapter 10 Classificatin f alchls (primary, etc ) Alchl nmenclature Dils, multifunctinal grups, etc Naming phenls Orth, meta, para phenls Jhn Cngletn, Orange Cast Cllege
Physical prperties f alchls Acidity f alchls Why is phenl mre acidic than cyclhexanl? Synthesis f alchls (knw mechanisms & sterechemistry) S N 2 reactins (chp 6) Acid-catalyzed hydratin (8-4) Oxymercuratin-demurcuratin (8-5) Hydrbratin-xidatin (8-7) Synthesis f dils (8-13, 8-14) Additin f acetylides t carbnyls (9-7) Grignard reactin (knw mechanism & sterechemistry) with carbnyl cntaining cmpunds (10-9) Organlithium reactins (knw mechanism & sterechemistry) with carbnyl cntaining cmpunds (10-9) Reductin f carbnyl using NaBH 4 and LAH (knw mechanism & sterechemistry) Knw the sterechemistry here Which reagent is mre selective? Chapter 11 What is meant by xidatin and reductin? Oxidatin f alchls with Na 2 Cr 2 O 7 /H 2 SO 4 Knw mechanism Where des xidatin stp? Oxidatin f alchls with pyridinium chlrchrmate (PCC) Knw mechanism Where des xidatin stp? Dn t wrry abut the ther many methds f alchl xidatin in sectin 11-3. Bilgical xidatin Fate f ethanl, methanl, ethylene glycl in the bdy What is the bilgical surce f hydride? Frmatin f tsylate esters frm alchls. Knw structure f para-tluenesulfnyl chlride Knw mechanism & sterechemistry Why is OTs - a gd leaving grup? Review S N 1, S N 2, E1, and E2 reactins, since any f these can ccur with a gd leaving grup. Alchls with hydrhalic acids (H-Br and H-I) Knw mechanism & sterechemistry 2, 3 alchls react via S N 1 1, 2 alchls react via S N 2 Alchls with hydrchric acid/ ZnCl 2 (Lucas reagent) Knw mechanism & sterechemistry (frmatin f a carbcatin) 1 alchls d nt react 2, 3 alchls react thrugh S N 1 mechanism Reactin f alchls with phsphrus halides Knw mechanism & sterechemistry Can use PBr 3, PCl 3, and P/I 2 Reactin des nt wrk n tertiary alchls (see mechanism t understand why ) Reactin f alchls with thinyl chlride Knw mechanism & sterechemistry Reactin des nt wrk well n tertiary alchls (see mechanism t understand why ) Retentin f cnfiguratin Dehydratin f alchls Knw mechanism & sterechemistry What needs t be in excess in rder t shift the equilibrium t the alkene? Jhn Cngletn, Orange Cast Cllege
Bimlecular dehydratin t frm ethers (see als chapter 14-7) Knw mechanism Lw temp usually needed here. Skip 11-11, 11-12, 11-13 Hw can yu frm an alkxide? (sectin 11-14) Na, K, r NaH Williamsn-Ether synthesis (knw mechanism) Chapter 13: Nuclear Magnetic Resnance Spectrscpy Upfield, dwnfield, chemical shifts Splitting, (n+1) rule Integratin Calculate the index f unsaturatin Number f peaks expected Be able t determine a structure given a 1 H-NMR and a mlecular frmula Skip all 13 C-NMR material Chapter 14; Ethers and Epxides Physical prperties f ethers Nmenclature f ethers Cmmn names IUPAC names Nmenclature f cyclic ethers Epxides Name as xirane Name as epxy Knw structure f xetane, furan, THF, pyran, THP Williamsn-ether synthesis (knw mechanism) Synthesis f ethers via xymercuratin-demurcuratin Knw mechanism & sterechemistry Knw reagents used Knw sterechemistry t Bimlecular dehydratin f alchls Knw mechanism (we did this in chapter 11 als) Cleavage f ethers using H-Br and H-I Knw mechanism What happens if ne f the ether substituents is a phenyl? Skip sectin 14-9, 14-10, 14-16 Synthesis f epxides Knw perxyacid mechanism & sterechemistry (review chapter 8) What is MCPBA? Knw base-prmted epxide frmatin What rientatin is needed here? Acid-catalyzed ring pening f epxides Using H 2 O and an acid: Knw mechanism & sterechemistry Using alchl and an acid: Knw mechanism & sterechemistry Using H-Cl, H-Br, r H-I: Knw mechanism & sterechemistry What is the rientatin f ring pening here? Base-catalyzed ring pening f epxides Knw mechanism (alkxide) & sterechemistry Knw mechanism (Grignard reagent) & sterechemistry What is the rientatin f ring pening here? Jhn Cngletn, Orange Cast Cllege