CHEM 234, Spring 2015 Second Midterm ANSWER PRINTED FIRST NAME Ian R. Gould KEY PRINTED LAST NAME ASU ID or Posting ID Person on your LEFT (or Aisle) Person on your RIGHT (or Aisle) synth 1__________/20......................... • PRINT YOUR NAME ON EACH PAGE! rxns 2__________/36........................ • READ THE DIRECTIONS CAREFULLY! ether 3__________/18.......................... • USE BLANK PAGES AS SCRATCH PAPER mxn 4__________/38.......................... work on blank pages will not be graded... Grignard 5__________/21 ......................... •WRITE CLEARLY! peri 1 6__________/18......................... • MOLECULAR MODELS ARE ALLOWED peri 2 7__________/24......................... • DO NOT USE RED INK • DON'T CHEAT, USE COMMON SENSE! Total (incl Extra)________/175+5 Extra Credit_____/5 H He Li Be B N O F Ne Na Mg Al Si P S Cl Ar Ga Ge As Se Br In Sn Sb Te I K Ca Rb Sr Cs Ba Sc Ti V Y Cr Mn Fe Co Ni Cu Zn Zr Nb Mo Tc Ru Rh Pd Ag Cd Lu Hf Ta W small range range of values broad peak Re Os Ir Pt Au Hg O H C N N H C O C Tl Pb Bi Po At H C C N C Rn Me/Et 1600–1660 10 200 R C OH Approximate Coupling Constants, J (Hz), for 1H NMR Spectra H H H ~7 H H ~10 C C OR 1735 CH ~8 H 1600 O NR2 H O C CH3 –H2C NR2 7 140 6 120 5 100 Aromatic CR2 C CH 4 80 3 60 RC CR Alkyl 3Y > 2Y > 1Y 2 40 –OCH2– R C N R2C H ~15 C C 1500 C CH2 8 160 ~2 H C –OCH2– NMR Correlation Charts H H 1650 2000 ~2 C C O Aromatic Ar H mainly 8 - 6.5 O C ~2.7 1680 C 2500 9 180 t-Bu/Me O 1710 3000 11 220 O ~1.1 ~2.9 N –H2C X (δ, ppm) ~0.95 i-Pr/Me C C 2200 amine R NH2 variable and condition alcohol R OH dependent, ca. 2 - 6 δ O C H Et/Me ~2.6 C C C O C O H O R C OH ~1.4 H 2850–2960 3500 ~0.9 C broad ~3000 (cm-1) Me/Me H broad with spikes ~3300 broad ~3300 Me/Me O 2200 O H H/Me Xe C 2720–2820 2 peaks 3000– 3100 N H Kr H C 3300 ~1.0 Infrared Correlation Chart H Gauche Eclipsing H/H usually strong O C H Interaction Energies, kcal/mol 1 20 0 0 Alkyl 3Y > 2Y > 1Y C X C NR2 -2- CHEMISTRY 234, Spring 2015 MIDTERM #2 NAME There is no need to ask Dr. Gould or any of the TAs, there is NO NOMENCLATURE problem on this test! Question 1 (20 pts.) Show how you would make the target compond on the right from the starting compound on the left. Show reagents and conditions where appropriate, and the structures of important intermediate compounds. Do not show any (arrow pushing) mechanisms. Ignore stereochemistry. O PCC NBS/hν OH Br 1. BrMg K+ –O-t-Bu 1. BH3.THF 2. –OH/H2O2 O OH PCC 2. H3O+ H Extra Credit Question (5 pts.) In which kind of biomolecule can a photochemical 2 + 2 cycloaddition reaction take place DNA phospholipid carbohydrate protein -3- CHEMISTRY 234, Spring 2015 MIDTERM #2 NAME Question 2 (36 pts) Give the major organic products of the following reactions, indicate the stereochemistry using wedged/dashed bonds as appropriate and be sure to indicate the presence of any racemic mixtures. State whether a solution of the product(s) would be optically active or not, with a very brief explanation. HO O Na+ –OEt optically active H a) H single enantiomer EtO EtOH Cl 1 Equiv. HCl b) (±) NH2 NH2 c) NOT optically active racemic mixture CF3 Δ + (±) NOT optically active racemic mixture CF3 O Ph 1. Excess Ph-MgBr O d) OH OH Ph 2. H3O+ NOT optically active achiral Question 3 (18 pts) Draw the structures of the alcohol, the deprotonated alcohol and alkyl halide in the appropriate boxes you would use to complete the best WIlliamson ether synthesis of the provided ether, and fill in the base reagent required to deprotonate the alcohol NaH base OH O + Br O Na alcohol deprotonated alcohol alkyl halide -4- CHEMISTRY 234, Spring 2015 MIDTERM #2 NAME Question 4 (38 pts.) For the following reaction, give a full curved-arrow pushing mechanism for formation of products A and B. Indicate the Lewis acid and base at each step (LA or LB) and whether they are also Bronsted acids and bases (BA or BB). Include all reasonable resonance contributors for any intermediates AND INDICATE THE MAJOR RESONANCE CONTRIBUTOR as APPROPRIATE! OCH3 Br H H3CO CH3OH (solvent) + (±) (±) B A LA/BA HBr cat. OR... LB/BB CH3LA/BA LB/BB Me H H O O H O Me H LB H Me H3C Me O O H LB LA/BA O H H H O H Me LB/BB LA MAJOR number of steps in the mechanism for product A number of steps in the mechanism for product B 3 3 b) Indicate which product, A or B, would be formed under thermodynamically controlled conditions and which would be formed under kinetically controlled conditions and give a BRIEF explanation of the role of temperature in determining kinetic and thermodynamic control kinetic = A, thermodynamic = B, B is more likely to be formed at HIGH temperature since higher temperature enables REVERSIBLE reactions and allows the reaction to explore the entire reaction energy surface and find the lowest energy product, at low temperatures the reactions are irreversible and the fastest formed product is the major product c) Draw an energy diagram for formation of both A and B ON THE SAME DIAGRAM, clearly indicate which curve refers to formation of A and which to formation of B. B Energy A A H3CO + CH3OH + CH3OH OCH3 B reaction coordinate -5- CHEMISTRY 234, Spring 2015 MIDTERM #2 NAME Question 5 (21 pts.) In the provided structure, identify THREE carbon-carbon bonds that can be made using a Grignard reaction, give the structures of the Grignard and the molecule that it reacts with, acid workup steps (H3O+) are assumed you do not need to include them. CLEARLY indicate the C-C bond you are making in each reaction with an arrow O MgBr O + + OH H OH Me–MgBr OH O + H BrMg Question 6 (18 pts) For the following electrocyclic ring closure reaction F3C D CF3 use THIS structure for the drawing of the HOMO D D D heat F3C D CF3 H F3C H CF3 D use THIS structure for the curved arrow-pushing a) give the curved arrow-pushing that describes the bond-making and bond breaking b) on TOP of the reactant, draw a representation of the wavefunction of the HOMO usign the approximate "p A.O." method (assume that the structure is slightly tilted so that you can see the phases of the orbital c) does the allowed reaction proceed via a conrotatory or disrotatory ring closure? disrotatory __________________________ -6- CHEMISTRY 234, Spring 2015 MIDTERM #2 NAME Question 7 (24 pts). Give the ALLOWED product of the following cycloaddition reaction CN * heat + * CN A B CN CN * * OR CN CN not optically active, MESO compound a) Give the curved arrow-pushing that describes the bond-making and breaking. b) Redraw the cation A and give a pictorial representation of the wavefunction of the HOMO ON TOP OF THE STRUCTURE c) Redraw the dicyanoethylene B and give a pictorial representation of the wavefunction of the LUMO ON TOP OF THE STRUCTURE bonding CN bonding CN d) Is the allowed reaction suprafacial/suprafacial or suprafacial/antarafacial, give a brief explanation based on your drawings of the molecular orbitals, you MUST include the following terms: HOMO, LUMO, transition state the ALLOWED product of the reaction must have two bonding interactions in the transition state, consideration of the wavefunctions of the HOMO and the LUMO indicates that suprafacial/suprafacial reaction is allowed, thus the 2 -CN groups start cisand are on the same side in the product, and the two Me-groups on the outside of the cation end on the same side in the product e) Indicate ALL of the chiral/asymmetric centers in the product of the reaction using the * symbol, and explain whether a solution of the product would be optically active or not and why or why not
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