The Grignard reagent produced would be destroyed by the reaction
Transcription
The Grignard reagent produced would be destroyed by the reaction
216 S11-E2 Page 2 Name ________Key______________ I. (9 points) Answer in the boxes below the following questions for the Grignard reagent CH3-MgBr. (1) (2 points) Is the carbon atom associated with magnesium electrophilic or nucleophilic? electrophilic nucleophilic [circle one] (2) (3 points) Explain why the Grignard reaction has to be carried out in an anhydrous solvent. The Grignard reagent produced would be destroyed by the reaction with water present in a non-anhydrous solvent. (3) (4 points) Write the conjugate carbon acid (i.e., C-H) of the CH3– MgBr and explain why Grignard reagents are strong bases. structure: H H C H H explanation: The pKa of CH4 is ca. 50. Therefore, its conjugate base is highly basic. II. (6 points) Ethyl alcohol (C2H5OH) quite often is present in technical-grade diethyl ether. If this grade of diethyl ether were used, what effect, if any, would the ethyl alcohol have on a Grignard reagent used? Explain using a chemical equation using methylmagnesium bromide as an example. explanation based upon the reaction mechansim: A Grignard reagent formed would deprotonate H of the ethyl alcohol OH. H R OCH2CH3 R H MgBr + BrMg OCH2CH3 III. (8 points) For each of the reactions below, draw in the boxes provided the structure of the expected major organic product. (1) OH 1. Mg (1.1 mol equiv) ether Br 2. H3C aq NH4Cl (acidic workup) CH3 O (1.1 mol equiv) 4 + enantiomer (2) Mg (1.1 mol equiv) ether Br aq NH4Cl (acidic workup) OH CH3 O MgBr O 4 + enantiomer 216 S11-E2 Page 3 Name _______Key_______________ IV. (16 points) For the following reaction sequence, draw the correct structures in the boxes provided. + Ph3P: CH3 Br (C18H15P) benzene, reflux O CH3 Ph3P Br O 4 "salt" trans H H O NaOC2H5 /C2H5OH CH3 H H 4 major isomer: C12H12O + H H O H O O dichloromethane room temperature H CH3 Ph3P H cis H H 4 C21H19PO (ylide) + NaBr + C2H5OH CH3 4 minor isomer: C12H12O + note: Ph = C6H5 Ph3P=O V (12 points) Show how many peaks you would expect to observe in the proton-decoupled 13C NMR spectrum of each of the following compounds. Indicate your answers in the boxes provided. O (1) (2) CH3 H3C -OOC chiral center! O (3) S S NH3+ HO 7 6 (4) COOH (5) 7 (6) H3C COOH 180° rotation cis CO2H CO2H CH3 COOH 6 COOH 5 O CH3 O CH3 O H3C 5 216 S11-E2 Page 4 Name ________Key_____________ VI. (5 points) The proton NMR spectrum of a mixture of acetonitrile (CH3C≡N), methylene chloride, (CH2Cl2) and benzene (C6H6) is integrated and results in step heights of 15, 6, and 18 mm for the signals at δ 2.10, 5.30, and 7.26 ppm, respectively. In what mole ratio are the three substances present? No explanation required. No partial credit will be given to this problem. acetonitrile : methylene chloride : benzene = 15 : 3 6 2 : 5 18 : 6 : 3 3 VII. (8 points) For each of the reactions given below, draw in the box the structure of the expected product. Make sure to indicate the stereochemistry of the product whenever applicable. (1) O OCH3 + O H CH3O CH2Cl2 (solvent) H O + enantiomer O room temperature H O O endo product (2) H H O H + O CH2Cl2 (solvent) H room temperature H 3C 4 CH3 + enantiomer H CH3 H or HO endo product 4 VIII. (10 points) Provide in the box below a step-by-step, curved-arrow mechanism for the formation of hydroxy acid 2 from diketone 1. Make sure to include the mechanism for the acidic workup as well. O O mixture of stereoisomers here KOH ( 4 mol equiv) H2O H3O+ reflux to pH = 1.0 OH OH 1 2 mech arrows: 1 pt O O O 1 O O mech arrows: 1 pt interm str: 1 pt each 2 H mech arrows: 1 pt OH O O 1 H H O O OH OH This is fine, too. O O mech arrows: 2 pts O O OH H O mech arrows: 1 pt O OH H O H O H 216 S11-E2 Page 5 Name ________Key_____________ 216 S11-E2 Page 6. Name __________________________ IX. (continued) O A O C O O E O B D O F G Br O H O O O X. (15 points) On the basis of its spectroscopic information provided below, propose the structure for the compound, C5H12O. Draw the proposed structure in the box on page 7 and give a brief explanation as to how the structure is deduced from the spectroscopic information provided. Structure: H H3C H C C H3C OH CH3 chiral center! diastereotopic methyls 5 0 unit of unsaturation Explanation (just assign the IR peak at 3368 cm-1 and all H-1 peaks right next to the corresponding functional group/H-1 nuclei): 3.55 ppm (multiplet) 3368 cm-1 H H3C 0.92 ppm (doublet) 0.88 ppm (doublet) H H3C C C O CH3 H 1.92 ppm 1.3 ppm (doublet) 1.6 ppm (octet) 10 216 S11-E2 Page 8 Name ________Key_____________ XI. (15 points) On the basis of its spectroscopic information provided below, propose the structure of the compound, C10H16O4. Draw the proposed structure in the box on page 9 and give a brief explanation as to how the structure is deduced from the spectroscopic information provided. Make sure to assign all proton and C-13 NMR peaks. 216 S11-E2 Page 9 Name ________Key_____________ XI. (continued) Structure: H 3C H 3C CH3 CH3CH2O O OCH2CH3 O O OCH2CH3 O CH3CH2O H 3C OCH2CH3 CH3 H3C O OCH2CH3 O These should show only one sp2 alkene C-13 peak. => -1 point 5 Explanation (just assign the strongest IR peak and all H-1 and C-13 peaks right next to the corresponding functional group/H-1, C-13 nuclei): Units of unsaturation: 3; only 6 C-13 peaks! 2.0 ppm H 3C 1725 cm-1 4.2 125 ppm ppm 14 ppm 156 O ppm 1.2 ppm OCH2CH3 22 ppm 60 ppm H 3C 2.0 ppm OCH2CH3 O 1725 cm-1 167 ppm 14 ppm 4.2 ppm 10