ORGANIC CHEMISTRY I
ORGANIC CHEMISTRY I CHEM 331
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This 11 page Class Notes was uploaded by Columbus Torphy on Sunday September 27, 2015. The Class Notes belongs to CHEM 331 at Iowa State University taught by Staff in Fall. Since its upload, it has received 209 views. For similar materials see /class/214550/chem-331-iowa-state-university in Chemistry at Iowa State University.
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Date Created: 09/27/15
N L Chem 331 Review New CC bond a R2CuLi R CHZX gt R CHZR b RCECH 5 Roz CfNa x Roz CCHZR39 3 via 3N2 Halogenation usually not synthetically useful due to mixtures an exception Br2 CH33CH v gt CH33CBr Alkenes handy stepping stone to many compounds a Preparations l Dehydrohalogenation C Clt alc h 1 CC E2 anti elimination KOH H X 2 Dehydratlon i5 CC carbocation rearrangements OH H A possible H2 R R39 3 RCECR39 cc 39 39 Lindlar Catalyst H H Syn addmon 39 Na R H 4 RC ECR gt Czc ant1 addition NH3 H R39 b Alkenes as a synthetic tool C12H20 1 CC t39 dd39t39 or BrZHZO an 1 a 1 ion OH C1Br HCl 2 C C or HBr Markovnikov s rule H ClBr H 0 3 RCHCH2 3 gt RHCH3 carbocation rearrangements possible OH 1 Chem 331 Review continued 1 HgOAc2H20 4 RCHCH2 W RHCH3 no rearrangements OH 1 BH3THF RCH CH OH antiMarkovnikov addition 5 RCH CH2 DHZOZOHi 2 2 Br Br I 2 l alcoholic KOH 6 C C gt C C E CCl4 1393 2 NaNH2 C C 1 OsO 4 7 C C C C 2 NaHSO3H2 I I syn addition OH OH 8 gtCClt CHCl3 m C C syn addition 01 C1 C C 9 CC CHI gt syn additlon 2 2 ZnCu CH2 NBS 1 h 139 10 H2CCHCH2CH3 T H2CCHCHBrCH3 gt H20CHCHCH2 4 Alcohols a Preparation of Alcohols l Preparations from alkenes Preceding Section 3b Reactions 3 5 2 Reactions of RX via 8N2 DMSO OH RCHZX gt RCHZOH nonprot1c solvent b Reactions of Alcohols to form good leaving groups 1 R3COH HX gt R3CX good for 30 alcohol 2 ROH SOC12 or PCl3 gt RCl can also use the bromide 3 ROH TsCl gt ROTs 2 Chem 331 Review continued 4 Pre aration of P C O 1 0 R H a RCHCH LU gt 00 2 2ZnH20 H C O H H20H2304 b RCECH gt RCCH3 catHgSO4 ICI 1 BHTHF H c RCECH L gt RCHZC 2 H202 OH 0 1 4 V39 9 gt1 9 0 CH3CH2CHCH3 C1 CH3CH2 ICHCH3 OH CH3 2C CH2 CH32CHCHCH2 H H CH32CCH2 CH32CHCHCH2 CH32CCH2 Chem 331 Review alcoholic KOH for 1 ORXshould use KO t Bu to minimize SNZ H2804 or H3PO4 0r H HX where X Cl Br or I HX where X Cl Br or I 1390014 Br2 gt H20 H20H3Po4 gt 1 HgOAc2H20 2 NaBH4 NaOH 1 BH3THF 2 HZOZOH CHCI3 i BuO Kt SimmonsSmith Reagent CH212 ZnCu 1 CH CHCHCH m 139quot 3 3 product minor CH3CH2CH CH2 product same products as above X I CH3 ZCCH3 M arkovnikov 39s Rule CH32CHCHCH3 and X m CH32CH20H3 rearranged X carbocation anti addition H Br CH32 ICCHZBr OH CH32CHCHCH3 and OH CH32CH2CH3 OH rearranged carbocation CH32 ICCHs OH syn addition UI 0 CH3 CH3 Q CH32C CHCH3 CH32C CHCH3 CH32C ICHCH3 OH OH Cl H2C CH CH3CH CH2 HCE CH CH3CE CH CH3CECCH3 H2 cat PdC l 0s04 2 NaHSO3H20 1 03 2 zmH20 KMnO4 H30 heat H104 H20 Per0X1des gt 1 l3r2CC14 2 Alcoholic KOH or 2 NaNHZ 3 NaNHZliq NH3 liq NH3 1 NaNHZliq NH3 2 CH3CH2C1 must be 1 ORX excess of HCl excess BrZCC14 2 syn addition H H syn addition H H H CH32CO CH3CO OH CH32CO CH3CO H CH32CO CH3CO lCl CHz C a polymer CH3CE CH HCECCHZCH3 3612 N C1 I ollows CH3CCH3 M arkovnikov 39s I Rule C1 CH3CBr2CBr2CH3 22 23 24 25 26 28 29 LA 3 LA CH3CE CH CH3CE CH CH3CE CCHZCH3 CH3CE CCHZCH3 CH3CE CCHZCH3 CH3 CH3 C C H H HCE CCHZCH3 CHs CH3 lC CH3 H CH3CH2CH CH2 CH33COH CH3CH20H CH3CH20H CH3CH2Br H20 cat HgSO4HZSO4 1 BH3THF 2 H202OH H2 Pt C catalyst H2Lindlar catalyst Li 0r Na liq NH Br2 CC11 KMnO4 or 03 gt conc HX where X 1 Br or Cl PC13 0r SOC12 gt PBr3 gt Mg ether 3 f l CH3 CH3 M arkovnikov39s 0 Rule H CH3CH2C 0 CH3CH2CH2CH2CH3 CH CHCH 3 2 3 syn H H addition CH3 H anti CC addition H CHZCH3 CH3 CH3 H Br Br H amp Br H H Br H3 anti addition 0 0 HC CH3CH2 C H OH O CH3 CH3 IC CH3 Br CH3C HCH CH2 and Br CH3CH CHCH2 Br CH33CX CH3CH2C1 CH3CH2Br CH3CH2MgBr 35 CH3CH3 H30 CH3CH2MgBr gt 1 Li 36 CH32CHBr 2 Cul CH32CHZCuL1 RCHZX CH32CHCH2R should be 10 halide CH3 30201 gt 37 CH32CH2CuLi O k Y J good leaving group 38 CH3CH20H this is TsCl CH3 CH 39 Hgt 39Clt C1 0H 3 quotISN2 R H 5 strong nucleophile H C H mverszon D D OH 40 CH3 SOZOCH3 gt CH3 803 CH3OH strong nucleophlle this group is OTS CH3 H O 9H3 9H3 T 2 41 HFC CI H C OH HOgtC H 5 weak nucleophlle 5 5 CHZCH3 CHZCH3 CHZCH3 SN Rx major product C H OH 42 CH33CCH2Br 2 5 CH32 ICCHchs rearranges to V1a S 1 form more N OC2H5 stable carbocation CH3 C1 7 CH3 H 43 gtSH SN2Rx 5 399 E 399 quotinversionquot H H H SH Ph 44 H CH3 alcoholic Ph CH3 ann Cl H KOH HC Ph elimination 4 alcoholic CH3CHZCHCH3 mrcoldluct 45 CH3CH2 CHCH3 p KOH OTs or Cl BrI CH3CH2CHCH2 m1nor product H3 H CH3 46 alcohollc gt only KOH product CH30H2 H CH3CH2 H anti elimznation H H 47 HZC CH CH CH2 rgt CH3CHCH CH2 12 addition Br CH3CHCHCH2Br 14 addition 3r BrZCC14 BrCH2 CHCH CH2 12 addition 48 H2C CHCH CH2 gt BrCHZCH CHCHQBT 14 addition CH3 P 39d CH 49 H20C CHCH2 0X1 es I 3 natural CH20CHCH2 1 rubber H H2CCHC 0 SH Diels Alder gt 50 H2CCHCH CH2 A 0 Reaction 5 REVIEW OF CHEM 331 REACTIONS Reactions should be the thing you study rst since they are important in not only the reaction section but also in mechanisms and synthesis Studying reactions also pays off since you will be expected to know these in 332 How to use this worksheet Fill in the bolded parts during SI When you are studying you can use the rest of the points to nd reactions that t the description There are a lot of words on hereidraw the reactions that I ve written about Types of reactions you know 1 Reactions of double bonds and sometimes triple bonds a Adding 2 things across a double bond b Formation of a double bond c Adding to the carbon next to a double bond NBS CCl4 d Cleavage at the double bond e Special things that pertain to conjugated double bonds i 12 and 14 products ii DielsAlder 2 Lightinduced reactions a Chlorination or bromination b NBShV 3 SNlSNZElEZ 4 Organometallic Reactions a Grignard b CuLi It s quot helpful to group reactions 139 to what theV are useful for in synthesis 1 Adding alkyl groups if the product has more carbons than the starting material a Add a primary alkyl halide to a terminal alkyne an SN2 rxn b CuLi and alkyl halide use this if you need to add to the middle of a chain 2 Stereospecific reactions a SN2 7 inverts IVS con guration b Reduction of a triple bond to a double bond i LiNH3 vs Lindlar c Markovnikovanti Markovnikov reactions d Reactions with a bromonium intermediate will add anti 3 Reactions that create certain functional groups a Carbonyls i Cleavage reactions double bonds triple bonds diols b Threemembered rings i Epoxides by peroxides acids and bases ii Cyclopropanes Simmons Smith and addition of CHC13 c Triple bonds d Double bonds e Halides from hydrocarbons lightinduced reactions f Alcohols g Cyclohexanes Diels Alder Practicing Reactions A helpful resource is the companion website for the 63911 edition of your textbook Google McMunray Organic Chem and it should be the rst hit I will also have a link on the SI website to the website The organic interactive problems in each chapter are extremely helpful Even if you don t use this to study for the nal it is a good quick and easy review after your ochemless summer months Make notecards Study them You have more than just the old nals at your disposaliyou can practice reactions off of any of the old exams 1 through 5 Mechanisms you know 1 Reactions that have a carbocation intermediate these follow Markovnikov s rule and are subject to rearrangement through resonance a Addition of HX to double bonds b SNlEl reactions especially when water or an alcohol is used 2 Reactions with a radical intermediate a Any light induced reactions C12 B12 01 NBS and hv b Know initiationpropagationtermination steps Intermediates and transition states you know 1 Carbocations see list of reactions above 2 Radicals see above 3 SNZSNlElEZ reactions 4 Bromonium ions addition of Br2 or Br2 and H20