CHEM 234, Spring 2015 Third Midterm PRINTED FIRST NAME Ian R. Gould PRINTED LAST NAME ASU ID or Posting ID Person on your LEFT (or Aisle) Person on your RIGHT (or Aisle) 1__________/13 ....................... • PRINT YOUR NAME ON EACH PAGE! 2__________/18......................... • READ THE DIRECTIONS CAREFULLY! 3__________/40......................... • USE BLANK PAGES AS SCRATCH PAPER 4__________/20......................... work on blank pages will not be graded... 5__________/20 ......................... •WRITE CLEARLY! 6__________/30......................... • MOLECULAR MODELS ARE ALLOWED 7__________/20......................... • DO NOT USE RED INK 8__________/14......................... • 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 2850–2960 Rn Me/Et 1600–1660 11 220 O 10 200 R C OH ~2.7 Approximate Coupling Constants, J (Hz), for 1H NMR Spectra H H H 1680 ~7 H OR H ~10 C C 1735 CH ~8 H 1600 O 2000 H O C CH3 –H2C NR2 7 140 6 120 5 100 R2C Aromatic CR2 C CH 4 80 3 60 RC CR Alkyl 3Y > 2Y > 1Y 2 40 –OCH2– R C N H ~15 C C 1500 –OCH2– C CH2 8 160 ~2 H NR2 1650 NMR Correlation Charts H H C 1710 ~2 C C O Aromatic Ar H mainly 8 - 6.5 O C t-Bu/Me O C 2500 9 180 ~1.1 ~2.9 N –H2C X (δ, ppm) ~0.95 i-Pr/Me C C 2200 3000 O C H Et/Me ~2.6 C C C amine R NH2 variable and condition alcohol R OH dependent, ca. 2 - 6 δ O R C OH ~1.4 H C O C O H 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- CHM 234, Spring 2015, Midterm #3 NAME Question 1 (13 pts). Give the IUPAC name for the following compound. Be sure to use cis/trans, E/Z or R/S where appropriate. O OH Question 2 (18 pts) For the electrocyclic ring-closure reaction shown below CH3 F3C heat H3C CH3 a) Draw the arrow-pushing to account for the reaction and draw the product b) How many electrons are involved in this reaction? c) Is the allowed product formed via a Huckel or a Mobius transition state? Briefly explain your choice in terms of the concept of aromaticity. d) Does the allowed reaction proceed via a CONROTATORY or DISROTARORY ring closure? BRIEFLY explain your choice. Extra credit question (5 pts). β-carotene is synthesized using which reaction? Clemmenson Grignard Wittig Aldol -3 - CHM 234, Spring 2015, Midterm #3 NAME Question 3 (40 pts.) Provide the missing major organic products or reagents/conditions as appropriate, you can IGNORE stereochemistry in these problems O SO3/H2SO4 a) O O O b) 1. PhMgBr O 2. Zn(Hg)/HCl/H2O O Na+ –OCH3 c) CH3OH O d) Br Br H O 1 Equiv. H2NMe e) O H+ cat. -4CHEM 234, Spring 2015 MIDTERM #3 NAME Question 4 (20 pts.) Synthesize the (target) molecules on the right from the starting molecules the left. this can not be done in one reaction. Give reagents and conditions and the intermediate molecules at each step. Do not show any mechanisms or transient intermediates. NO2 CO2H SO3H CHM 234, Spring 2015, Midterm #3 -5NAME Question 5 (20 pts.) Synthesize the (target) molecule on the right from the starting molecule the left. this can not be done in one reaction. Give reagents and conditions and the intermediate molecules at each step. Do not show any mechanisms or transient intermediates. O O OH -6- CHM 234, Spring 2015, Midterm #3 NAME Question 6 (30 pts.) For the following TWO reactions a) and b): 1) Give a complete arrow-pushing mechanisms 2) Indicate the lewis acid/base for each INTERmolecular step (LB or LA) and whether they are also Brønsted bases/acids (LB/BB or LA/BA) 3) Show where every proton comes from and goes to (i.e., no +H+ or -H+) 4) DRAW ALL RELEVANT RESONANCE CONTRIBUTORS FOR THE INTERMEDIATES MeOH (solvent) a) heat Br Give the number of steps in your mechanism for reaction a) _________ O b) H2O H2SO4 cat. OH OH Give the number of steps in your mechanism for reaction b) _________ -7- CHM 234, Spring 2015, Midterm #3 NAME Question 7 (20 pts) Give the curved arrow pushing mechanism for the following reaction, you do NOT need to indicate the acids/bases at each step, AND you can use the abbreviated +H+/-H+ notation, BUT you MUST include all important resonance contributors for the intermediates O N TsOH (cat.) H2N Question 8 (14 pts). Rank the following reactions in order of increasing equilibrium constant for formation of the acetal and give a BRIEF explanation O O A HO OH O O smallest HCl cat. O B HO H OH O H HO C O HCl cat. O OH HCl cat. < O O O < largest
© Copyright 2024