Review Topics for Final to obtain 2mols X2 Tetrahalide stable a SN2 backside attack for methyl or primary halides b E2 for bulky halides secondary or tertiary a Complete Reduction Catalyst Pd Pt or Ni Alkane b Lindlar s Catalyst Poisoned Pd BaSO4 Quinoline Cis Alkene c Metal Ammonia Na NH3 Trans Alkene Chapter 9 1 Formation of Acetylide Anions from Acetylene 2 Alkylation using Acetylide Anions ADDITION REACTIONS breaking pi bond to form two sigma bonds 3 Reduction of Alkynes Catalytic Hydrogenation breaking pi bond to form Hydrogen sigma bonds 4 Addition of Halogens Cl2 or Br2 mixture of Trans Cis Alkenes difficult 5 Addition of Hydrogen Halides HX 6 Addition of Water Hydration 1 mol vinyl halide alkene 2 mols geminal dihalide alkane Markovnikov a Mercuric Sulfate HgSO4 H2SO4 b Hydroboration Oxidation BSia2H H202 OH least substituted Carbon gets Hydrogen bond most stable most substituted Carbon gets Halide Halides go on same Carbon most substituted Hydrogens go on same Carbon least substituted Enol vinyl alcohol Keto Enol Tautomerism ketone or Markovnikov BSia2 Ketone Unstable Enol aldehyde Anti Markovnikov aldehyde Alkene OsO4 H2O2 or cold dilute KMnO4 OH Vicinal Diol in Syn Addition Cis Alkene Peroxyacid O double C OH epoxide H30 Vicinal Diol in Anti Addition Trans Alkene H H20 Carbon to Carbon adding H OH in Markovnikov Alkene 1 Hg OAc 2 H20 2 NaBH4 Carbon to Carbon adding H OH in Markovnikov trans Alkene 1 BH3 THF 2 H2O2 OH Carbon to Carbon Syn Addition of H OH in Anti Markovnikov a Syn Dihydroxylation b Anti Dihydroxylation Chapter 10 Alcohol Synthesis Forming Carbon to Carbon 1 Acid catalyzed Hydration 2 Oxymercuration Demercuration 3 Hydroboration Oxidation Forming Vicinal Diols 1 Dihydroxylation forming Vicinal Diols Forming Primary Alcohols 1 Nucleophilic Substitution on an Alkyl Halide Alkyl Halide OH Primary Alcohol 2 Addition to Ethylene Oxide Forming from Carbonyl Compounds 1 Addition to Carbonyl Compounds Organometallic Reagents formaldehyde primary alcohol aldehyde secondary alcohol ketone tertiary alcohol a Acetylide b Grignard Reagent c Organolithium Reagent Limitations ex OH NH SH C triple CH Acetylene NaNH2 Acetylide Ketone Alkoxide H3O Tertiary Alcohol Primary Alkyl Halide Mg ether Grinard Ketone ether Alkoxide H3O Tertiary Alcohol Primary Alkyl Halide 2Li LAH same as above presence of acidic protons strong bases will protonate presence of multi bonds w strong electronegative nucleophile ex C double O CN C triple N S double O N double O Ethylene Oxide Grinard ether or Organolitium Reagent Alkoxide H3O Primary Alcohol always yields primary extends carbon chain by 2 carbons and acids too stronger than NaBH4 2 Reduction of Carbonyl Compounds Hydrides Summary p 457 NaBH4 only works on aldehydes and ketones LAH works on those and esters aldehyde primary alcohol ketone secondary alcohol Ketone NaBH4 ether or LAH Alkoxide H3O Secondary Ester or Acid LAH Alkoxide H3O Primary Alcohol always yields primary adds 2 Hydrides Alcohol Carboxylic Acid 1 Chromic Acid Na2Cr2O7 H2SO4 2 NaOCl Chapter 11 Reaction of Alcohols 1 Oxidations Primary Aldehyde 1 PCC 2 Swern DMSO COCl 2 low temp 3 DMP mild conditions Secondary Ketone 1 PCC 2 Swern DMSO COCl 2 low temp 3 DMP mild conditions 4 Chromic Acid Na2Cr2O7 H2SO4 5 NaOCl Can t Oxidize Tertiary 2 Substitution to form Alkyl Halides 3 Dehydration Reactions 4 Ester Synthesis a Fischer Ester Synthesis b Acid Chloride R OH TsCl pyridine R OTs R OH HX R OH H R OH2 X R X OTs Water are good leaving groups OH is a poor leaving group secondary and tertiary go through SN1 primary go through SN2 limitations R OH PX3 R OH PX2 R OHPX2 X R X PCl3 or PBr3 OHPX2 is a good leaving group good yields with primary and secondary alcohols competition with elimination rearrangements of carbocation limited ability to make alkyl halides H2SO4 low temp 140 2 moles of alcohol ether substitution high temp 180 alkene elimination usually E1 rearrangements rate of reaction 3 2 1 not good for converting primary to alkene Pinacol Rearrangement Vicinal Diol pinacol H2SO4 heat ketone pinacolone one hydroxy group turns into the double bonded O the other converts to methyl group R OH HO CR double O carboxylic acid H2SO4 equilibrium reaction seldom used RO CR double O ester water R OH Cl CR double O acid chloride RO CR double O ester high yields better reaction for making esters HCl 5 Williamson Ether Synthesis R O CH2 R NaX OTs R OH Na R O alkoxide ion R CH2 X or OTs alkyl halide primary alkyl halide SN2 secondary or tertiary Elimination