Name (Last, First, MI): Student ID Number: Chem 30C, Fall 2005 Final Exam Wednesday, December 14 Problem # Possible Points Points Awarded 1 45 2 24 3 8 4 8 a 5 6 8 i 6 8 8 9 14 10 12 1 14 12 = 20 13 14 14 14 Total 200 ***Do not open this exam until instructed to do so*** ***Write all answers in the boxes provided*** -16 Pages Follow-Problem 1. Draw the major product for the following reactions in the boxes provided. Show stereochemistry where relevant. For multi-step reactions give the final product only (ie. no intermediates). Unless otherwise noted, assume 1 equivalent (1 eq.) of reagent. If the product is a polymer, draw the repeat unit and the end groups. Assume for Diels-Alder reactions that all rules and preferences are followed. (3 points each) (Craw the product thet reeuits from {errinaion by radical chain couping: bo ‘sure to include bath end groups) ethylbenzene (PAOOz)2, Cy Problem 1 continues on the next page9 NO2 “HS, —— (Hint: Cope) Problem I continues on the next pageOo ~ + CH=CH ——> Problem I continues on the next pageTCH). -78°C oO nd 2 HOMO NaBH,Problem 2. Draw the reagent(s), intermediate or product in the box provided. (4 points each box) a FE F F F F ° F F F AIBN, heat (Draw only repeat unit; no end groups) b. 0 Bb neat — or N, Bea ee eeeee SS ° NaSCH,CHs Problem 2 continues on the next pageOH OH CO COOH Cle, FeClyProblem 3. In both drawings and words, explain how polyurethane foams for seat cushions, etc. are made. (8 points) Problem 4. Two Diels-Alder adducts are drawn below. Circle the one that would undergo reverse Diels-Alder at a lower temperature. Briefly explain your answer in the box below. (Hint: Draw the diene and dienophile.) (8 points) oO oO NCH INCHProblem 5. The following product was synthesized by Robinson annulation. In the box provided, draw the starting material(s) only (i.e. no intermediates) that would yield the given product. (5 points) Problem 6, Explain why cyclobutadiene is an especially unstable molecule. Draw the molecular orbital diagram to help explain your answer. (8 points)Problem 7. Which is most acidic and which is least acidic between p-chlorophenol, benzyl alcohol, and p-nitrophenol? Answer this question by drawing the structures in increasing order of least acidic (to left) to most acidic (to right) in box below. (6 points) Problem 8. Classify the following molecules as aromatic, antiaromatic or nonaromati Assume all molecules are planar. For each molecule state the number of pi electrons. Write your answers on the lines provided. (8 points) C* A classification: ——_—_ classification: pilectrons: a pi electrons:Problem 9. The following product was synthesized using malonic ester synthesis, starting from diethyl malonate (malonic ester). Provide the synthesis. Do not show the mechanism. (14 points) 10Problem 10, Provide a reasonable synthesis to carry out the following transformation, (12 points) ° 9 CHs CH, CH:CH,CH=CH, ulProblem 11. Starting from aniline, synthesize the following compound, using whatever reagents necessary. More points will be given for a synthesis that involve fewer steps that are higher yielding. (14 points) nNProblem 12, Below is the structure of D-Idose. Answer the following questions related to this monosaccharide. (20 points total) ‘a, You classify this monosaccharide as a: CH;OH D-ldose b. Draw the Haworth projection and conformation representation of the d-anomer of the 6-membered ring and name the resulting structure. | Haworth projection conformation representation Name: Problem 12 continues on the next page 1Bc. Subject the hemiacetal above to butanol and HCl. Draw the resulting compound as and name it. Draw the a-anomer Name: . Subject D-Idose to NaBH, in water. Draw and name the resulting compound. Name: e. Subject the product formed in c above to periodic acid. Draw the resulting product(s). 14Problem 13. Provide a synthesis of Ala-Ile starting from alanine (Ala) and isoleucine (lle). Throughout the synthesis, abbreviate the amino acids as H2N-Ala-COOH and H)N- Ie-COOH rather than drawing out the structures. Do not show the mechanism. (14 points)Problem 14. Provide a synthesis for the following polymer starting from dicyclopentadiene and using any other necessary reagents. Make sure you account for the polymer end groups in your synthesis. (14 points) 20 = Ot 16Name (Last, First, MI): Student ID Number: Chem 30C, Fall 2005 K ar Final Exam Wednesday, December 14 Problem # Possible Points Points Awarded 1 45 __ 2 24 3 8 4 8 Z 5 5 6 8 7 6 | 8 8 i 7 9 14 10 12 il 14 [ 20 14 14 14 Total 200 ***Do not open this exam until instructed to do so*** ***Write all answers in the boxes provided*** -16 Pages Follow-Problem 1. Draw the major product for the following reactions in the boxes provided. Show stereochemistry where relevant. For multi-step reactions give the final product only (i.e. no intermediates). Unless otherwise noted, assume 1 equivalent (1 eq.) of reagent. If the product is a polymer, draw the repeat unit and the end groups. Assume for Diels-Alder reactions that all rules and preferences are followed. (3 points each) ABN ain sm 8 (Craw the product tht reauts from termination by racical chain coupling: be ‘sure to include both end groups) oe ettytbenzene _NBS co (PROO,}a, CO's \ eA Problem 1 continues on the next pageCHC HOO, Hy HOH = a ‘SO; o N02 HS04 8 a7 ACs h heat Lb a HCO. (Hint: Cope) Problem 1 continues on the next pageNHe 4. NaNO», HCl, O°C fm LL L 2A L CO — Problem 1 continues on the next pageProblem 2. Draw the reagent(s), intermediate or product in the box provided. (4 points each box) a F F F F F ° F FE FE AIBN, heat (Draw only repeat unit; no end groups) Problem 2 continues on the next pageOH ‘COOH Cl, FeCls (oeProblem 3. In both drawings and words, explain how polyurethane foams for seat cushions, ete. are made. (8 points) tae eC From di Secganetes Qo smet deteant Cf Hyd vs ne pelgawn€etica leled Gueias te fein Cae bernie Gerd When AE comm pf of €F te (We tmirg 20CE cases The fenm Release of Cee Hee Romwscce Problem 4, Two Diels-Alder adducts are drawn below. Circle the one that would undergo reverse Diels-Alder at a lower temperature. Briefly explain your answer in the box below. (Hint: Draw the diene and dienophile.) (8 points) __-—— oOProblem 5. The following product was synthesized by Robinson annulation. In the box provided, draw the starting material(s) only (i.e. no intermediates) that would yield the given product. (5 points) Problem 6. Explain why cyclobutadiene is an especially unstable molecule. Draw the molecular orbital diagram to help explain your answer. (8 points) cies Ree av ge Cleclees RE wa nenkeassyy / cee 14 fryese Der penned # Let Nene TI mnie me mle cue POY ansteble dn pe Elbe se aoherenalic a behest pub oder vend UNstab&Problem 7. Which is most acidic and which is least acidic between p-chlorophenol, benzyl alcohol, and p-nitrophenol? Answer this question by drawing the structures in increasing order of least acidic (to left) to most acidic (to right) in box below. (6 points) IN CT HS AS so toy Problem 8. Classify the following molecules as aromatic, antiaromatic or nonaromatic. Assume all molecules are planar. For each molecule state the number of pi electrons. Write your answers on the lines provided. (8 points) {\ A mabe Acaaromehe classification: classification: 4 2 pi electrons: _ pi electrons:Problem 9. The following product was synthesized using malonic ester synthesis, starting from diethyl malonate (malonic ester). Provide the synthesis. Do not show the ‘mechanism. (14 points) | Melhe, GACH —_> by ae ro 1. Niele, FOC —> 2 Abr 1 Nood, ilo e > ENCE 2 Oo 10Problem 10. Provide a reasonable synthesis to carry out the following transformation. (22 points) CHa (CH,CH,CH=CH, [ VKoH od, heat Pee Laeeeu- aed reProblem 11. Starting from aniline, synthesize the following compound, using whatever reagents necessary. More points will be given for a synthesis that involve fewer steps that are higher yielding. (14 points) Miz Be c | | 12Problem 12. Below is the structure of D-Idose. Answer the following questions related to this monosaccharide. (20 points total) HO HO—+—H a. You classify this monosaccharide as a: H—}—0H HO—+—H hexos ton CH.OH D-ldose b. Draw the Haworth projection and conformation representation of the oL-anomer of the 6-membered ring and name the resulting structure. Haworth projection conformation representation Name: A~D-idepyrane Problem 12 continues on the next page 13¢, Subject the hemiacetal above to butanol and HCI. Draw the resulting compound as and name it. Draw the a-anomer Gc Si (on funation wy rok BC Hac Name: CRC OA 2C 4 3Problem 13. Provide a synthesis of Ala-Ile starting from alanine (Ala) and isoleucine (lle). Throughout the synthesis, abbreviate the amino acids as H2N-Ala-COOH and HN- Te-COOH rather than drawing out the structures. Do not show the mechanism. (14 points) Mp Sey e Es Hyw- Tle County Tle €'-caty 3 Aeng-cell-w-ala-Coow t Hee x dole ( Is - E-ue Tle -€ Cody a \ Hy > Cie (Ce L U Mea He Hz h- Ma-Tle-c cet pd 15Problem 14. Provide a synthesis for the following polymer starting from dicyclopentadiene and using any other necessary reagents. Make sure you account for the polymer end groups in your synthesis. (14 points) 16