Reactions Markovnikov Practice Problems and Keys Part 2

3. NaBH4 2) Circle the type of reaction occurring in each of the following. If more that one reaction type occurs label the major and minor product. Cl KI, Ether SN1 SN2 E1 E2 SN1 SN2 E1 E2 SN1 SN2 E1 E2 SN1 SN2 E1 E2 SN1 SN2 E1 E2 EtOH NaEtO SN1 SN2 E1 E2 MeOH MeOK SN1 SN2 E1 E2 SN1 SN2 E1 E2 SN1 SN2 E1 E2 SN1 SN2 E1 E2 SN1 SN2 E1 E2 Cl C C C C CH3ONa, CH3OH Cl CH3 MeOH, Heat Br C C C OH OH C C C HI POCl3 Cl CH3 C C C Br CH3 HAc, Heat Cl O H2SO4, H2O Cl KOH, EtOH C Cl C C C C tButOH, Heat 3) Please give the R,S and D, L designation for each of the following compounds, COOH H Cl CH3 H C CH3 H C COOH C OH Cl C CH3 CH3 OH R,S _______ _______ _______ D,L _______ _______ _______ HOOC C CH3 HO C CH3 Cl 3b) Which are enantiomers and which are diastereomers? Enantiomers = Diastereomers = 4) Please draw the complete mechanism for the Markovnikov addition of HCl to 3methyl butene. 5) Please give the complete mechanism of the halohydrin reaction caused by reacting 3-methyl butene with water and bromine. 6a) Please draw the product of the Saytzeff elimination of 3R, 4S 3-chloro-4-methyl hexane. 7) Please give the product of the Saytzeff elimination of HBr from the following compound. Show your work. C H3 C 2H5 C C H C 2 H5 H Br 8) Please draw the complete mechanism of the E1 elimination of 2-methylcyclohexanol using H3PO4 and heat. 9) Please draw the complete mechanism of the acid catalyzed addition of ethanol to 3methyl pentene. 10) Please give the complete mechanism of the anti-Markovinikov addition of HBr to butene. 11) Please give the mechanism for the formation of both products made by the reaction of t-butyl alcohol with HCl. 12) Please draw all of the products from the reaction of trans 2 butene with water and bromine (Halohydrin reaction). 13) Please give the complete mechanism of acid catalyzed epoxide ring opening using epoxy propane. 14) Please draw the reaction diagram for the anti-Markovnikov addition of HCl with PBA to butene, showing all reactants, products, intermediates and transition states. Do not show any chain termination steps. The first step is endothermic and all subsequent steps are exothermic. 15) Please draw the reaction diagram including all reactants, products, intermediates, and transition states for the SN1 reaction that occurs between cyclohexanol and HCl. The reaction is overall exothermic and the first step is rate determining. 16) Please draw the complete mechanism of the acid catalyzed addition of ethanol to propene. When you are finished draw the reaction diagram below. 17) What is the ratio of products formed by the free radical halogenation of hexane? Set it up. You do not have to solve it. 18) Please calculate the percentage of 1º and 2º products formed by the free radical chlorination of butane. 19) Predict the percentage of products made by the free radical chlorination of 1,1,4,4 tetramethylcyclohexane 1) Please supply the product for each of the following reactions. Cl C C HCl C C C Br CH3 Cl C C EtO /EtOH H3 C C Br H H C C EtO-/EtOH C C2H5 C C C C NaEtO, EtOH CH3 C C H3 C C 2 H5 1, Cl2, hv 2. tButO-, tButOH 3. KMnO4, H+, H2O C C OH C C HBr, MCPBA Br C O H C C CH3 C CH2O C CH3 C C C O O3, (CH3)2S C C CH3 H3 C C OH CH3 H CH3 H H C 2 H5 H I H C2H5 CH3 O C KI, Ether Cl H Br C C H H3 C C H3 C C C C CH3 C H OCH3 C - C CH3 CH3 Hg(OAc)2 CH3OH, NaBH4 C H2O, Br2 C C C MCPBA C C C CH3 C H C CH3 Cl HAc, Heat OsO4, H2 O2 H CH3 CH3 CH3 CH3 OH OH OH H con. H2SO4 con. H3PO4 Heat C C C 1. Hg(OAc)2 2. C2H5OH 3. NaBH4 C C C OC2H5 C Br HBr, PBA C C C C Br C C C C C C Br2, H2O C C Br H2O, Br2 CH3 C C C 2. tButOK, tButOH 3. O3, (CH3)2S C C OH H CH3 Br O CH2O C C Br C H2SO4, KBr H CH3 OH CH3 1. PBA C OCH3 C C C C C OH Acetic Acid, Heat C C 1. Hg(OAc)2 Br EtOH,  C I P/I2 C C C C KMnO 4, NaOH, H2O 2. H 2O 3. NaBH4 Br OH Br C No Reaction C Br C CH3 OH 2. H 2SO4, CH3OH CH3 C C 1) Br2, hv 2) tButOK, tButOH 3) NBS OH 1. Br2, light C CH3 C C C C CH3ONa, CH3OH C C C C OCH3 OH HI, DMSO CH3 CH3 I 1) PBA OH OH OH 2) H2SO4, CH3OH OCH3 C C C C C C C C CH3 C Cl Br CH3 C H C NaEtO, EtOH C No Reaction C C2 H 5 C C C C C C Cl C C CH3 C C H 3C C 2H 5 O 1, Cl2, hv 2. tButO-, tButOH 3. KMnO4, H+, H2O C CO2 IsoProK, IsoProH C KOH, THF C C C C NBS C C C C HBr, MCPBA C C C C C C C MCPBA C C C C Br C C Cl CH3 Cl CH3 C CH3 C C CH3 1) KOH 2) H2SO4, Heat C C Br Cl Br2, CH3OH H3CO Cl KMnO4 H2O, H2SO4 O C C C O OH CH3 O Cl C C KI, EtOH C C I C C C C C C C C C NaEtO, EtOH C C C OEt C C CH3 PBA C CH3 CH3 HAc, Heat C C CH3 O C C OH C C HCl, MCPBA Cl C OH CH3 Br C H NaEtO, EtOH Br 2 NBS 2 tButOK, tButOH C H OH OH C C H 3C O C OH C Br HBr Br CH3 H2O, Br2 C C HCl C C HO CH3 C O O KMnO4 H2SO4, H 2O C C C 1. Hg(OAc)2 2. C2H5OH 3. NaBH4 C C C OC2H5 2) Circle the type of reaction occurring in each of the following. If more that one reaction type occurs label the major and minor product. Cl KI, Ether SN1 SN2 E1 E2 SN1 SN2 E1 E2 SN1 SN2 E1 E2 Cl C C C C CH3ONa, CH3OH Cl CH3 MeOH, Heat Br C C roM ni C OH OH C C C HI POCl3 roMja SN1 SN2 E1 E2 SN1 SN2 E1 E2 SN1 SN2 E1 E2 E1 E2 E1 E2 Cl EtOH NaEtO roMja rM oni CH3 C C Br C MeOH MeOK SN1 SN2 rM oni roMja CH3 HAc, Heat SN1 SN2 roM ni Cl O H2SO4, H2O roMja SN1 SN2 E1 E2 SN1 SN2 E1 E2 E1 E2 Cl KOH, EtOH C roMja rM oni Cl C C C C tButOH, Heat SN1 roM ni SN2 roMja 3) Please give the R,S and D, L designation for each of the following compounds, COOH H Cl CH3 H C CH3 H C COOH C OH Cl C CH3 CH3 HOOC C CH3 HO C CH3 OH R,S __S,S__ __R,R__ D,L ___D___ Cl __R,S__ ___L___ ___D___ 3b) Which are enantiomers and which are diastereomers? Enantiomers = AB Diastereomers = AC, BC 4) Please draw the complete mechanism for the Markovnikov addition of HCl to 3methyl butene. CH3 C C C H H+ CH3 C H H CH3 C + C CH3 H CH3 C C C + Cl- CH3 C H H CH3 C C H Cl 5) Please give the complete mechanism of the halohydrin reaction caused by reacting 2-methyl butene with water and bromine. CH3 H3 C C H 3C C Br+ CH3 CH3 Br Br H3 C C C H OH- CH3 H3 C H C C CH3 OH H 6) Please draw the product of the Saytzeff elimination of 3R, 4S 3-chloro-4-methyl hexane. C Cl H C C H CH3 C Cl C2H5 CH3 H C C2H6 H C C Cl C 2 H5 C Cl H C C H CH3 CH3 C 2 H6 H H The chlroine and the hydrogen must opposite one another C Cl H C C2H5 Rotate the C2H5 back of the molecule H CH3 C 2 H5 H CH3 C 2 H5 CH3 7) Please give the product of the Saytzeff elimination of HBr from the following compound. Show your work. H3 C C 2H5 C H C 2H5 C H Br H C 2H5 H3 C C 2H5 H3 C H H Br Br C 2H5 H C 2H5 C 2H5 C 2H5 H H3C The bromine and the hydrogen must opposite one another Rotate the back of the molecule 8) Please draw the complete mechanism of the E1 elimination of 2-methylcyclohexanol using H3PO4 and heat. H OH O + H 2O H CH3 CH3 H+ H H CH3 H H CH3 CH3 Hydride Shift 9) Please draw the complete mechanism of the acid catalyzed addition of ethanol to 3methyl pentene. H C H C C C H C H+ C H H H H C C C C H C C H H H H C C C C H H C C C2H5OH H H+ + H H C C C C H H C O H C C 2 H5 H H C C C C C H H O C 2 H5 C H 10) Please give the complete mechanism of the anti-Markovinikov addition of HBr to butene. O C O O OH C O + HBr light C Br + C C C OH Br C C C H2O + Br Br C C C C C HBr C C C H C C C + Br 11) Please give the mechanism for the formation of both products made by the reaction of t-butyl alcohol with HCl. H H OH C C C H+ C C C O H C C E1 C C C C H C C C H H + H+ C H C Cl H C C C H H 12) Please draw all of the products from the reaction of trans 2 butene with water and bromine (Halohydrin reaction). Br C H H C C C R,S OH Br C H OHH C C C Br+ Top C H C H C C H C Br C C H Br+ Bottom C H C C R,S OH Note: The R,S confgurations are based on the carbon with the OH C H C H C OH C C H C S,R Br OH- Br C H OH C C H C S,R Br 13) Please give the complete mechanism of acid catalyzed epoxide ring opening using epoxy propane. H O C C CH3 H+ OH O C C CH3 H2O C OH C CH3 O H H C C CH3 + H+ O H 14) Please draw the reaction diagram for the anti-Markovnikov addition of HCl with PBA to butene, showing all reactants, products, intermediates and transition states. Do not show any chain termination steps. The first step is endothermic and all subsequent steps are exothermic. O C O OH HO Cl HCl C C C C H Cl Energy C O C C O C C OH + HCl O H 2O + Cl O C Cl C OH C C Cl C C HCl C C C Cl H C C C C + Cl Reaction Coordinate 15) Please draw the reaction diagram including all reactants, products, intermediates, and transition states for the SN1 reaction that occurs between cyclohexanol and HCl. The reaction is overall exothermic and the first step is rate determining. H+ OH H H O H H H H H H H H H Energy H O H OH H H H H H H H H + H2O H H + H+ H Reaction Coordinate 16) Please draw the complete mechanism of the acid catalyzed addition of ethanol to propene. When you are finished draw the reaction diagram below. H+ C C H C C C C C OH C H C C C C O C C C C O C H Energy H C C C C + C + H C + C C OH H C H H C C C C O C + H Reaction Coordinate 17) What is the ratio of products formed by the free radical chlorination of hexane? Set it up. You do not have to solve it. X 100-X = 6 (1º) x 1.0 8 (2º) x 3.5 X = 17.65% 1º and 82.35% 2º 18) Please calculate the percentage of 1º and 2º products formed by the free radical chlorination of butane. X 100-X = 6 (1º) x 1.0 4 (2º) x 3.5 X = 30% 1º and 70% 2º 19) Predict the percentage of products made by the free radical chlorination of 1,1,4,4 tetramethylcyclohexane X 100-X = 12 (1º) x 1.0 8 (2º) x 3.5 X = 30% 1º and 70% 2º +