THE COLLEGE OF THE BAHAMAS EXAMINATION SEMESTER 01-2004 FACULTY OF PURE AND APPLIED SCIENCES SCHOOL OF NATURAL SCIENCES AND ENVIRONMENTAL STUDIES X NASSAU O FREEPORT OEXUMA O ELEUTHERA DATE AND TIME OF EXAMINATION: Tuesday, 20” April, 2004 at 7:00 p.m. DURATION: 3 HOURS COURSE NUMBER: Chem 230 COURSE TITLE: Organic Chemistry | STUDENT NAME: STUDENT NUMBER: LECTURER'S NAME: Dr. D. Davis INSTRUCTIONS TO CANDIDATES: This examination paper consists of 12 questions on 6 pages (excluding this instruction page). Answer ALL questions in the spaces provided on the examination paper. Only handheld calculators are allowed during this examination. The use of any other electronic device, e.g., cellular phones or PDA's, is strictly prohibited.Chemistry 230 Final Examination Semester 01-2004 Page | of 6 1. Shown below is the structure of the antibiotic penicillin V. With regard to the structure answer the questions below ayy CH KYSor oS COOH (a) Identify and label with an asterisk all of the stereocenters in the molecule. Ensure that your asterisks are not ambiguously placed. You will lose 0.25 marks for each incorrectly labeled atom. (b) What is the maximum number of possible stereoisomers for penicillin V? [3 marks] 2. Give the systematic names, including stereochemical designation (R, S, cis or trans, etc.) where required for the following molecules: OH oo > oo a cr HO. Cl o Ir @ wen ° NH, O 3 [4 marks] 3. Draw the chemical structure, showing stereochemical designation (R, S, cis or trans, efc.) where required, for the following molecules: (a) 2-nitro-4-propyltoluene (b) — (2R,35)-3-bromo-2-chlorobutanamide (0) cis-oct-4-en-2-one (4) ethyl-2-[(GR,4R)-3,4-dihydroxycyclohexyl]ethanoate [4 marks]Chemistry 230 Final Examination Semester 01-2004 Page 2 of 6 4. Assign priority numbers to the following groups. Let the number 4 represent the group of lowest priority and the number I represent the group of highest priority -~COOH @® (} -SH » ©) O a oO -CH,N(CH,), -CH,NHCH, Poon CO CO CO -SCH, -CH,OH -OH oe ee -CH,CH=CH, -C=N -CH=CH, [em eee (Oe) eee CR) ODO fo [4 marks] 5. Write the complete chemical name that represent the following: (@) enantiomer of (25,4R)-2,4-dichlorooctane (b) two diastereomers of (25,4R)-2,4-dichlorooctane [3 marks] 6. A solution of (2R,35)-2,3-dibromocyclohexanone has a specific rotation of -42.7° at 25°C (a) What is the specific rotation of a solution of (2R,35)-2,3-dibromocyclohexanone and its enantiomer at 25°C in which the %ee of the (22,35) enantiomer is 15%? (b) What is the percentage of each enantiomer in the solution in part (a)? [4 marks}Chemistry 230 Final Examination Semester 01-2004 Page 3 of 6 7. Add reagents and/or products as required to complete the following reactions. Show stereochemistry where applicable. @ ) © @ © (g) (h) @ @ CH3, H,SO, pee H,0 CH Om Hye oH + — Hye Hs + ae oO * — Ho OH + — Q + —+ oO uyc7ScI AICI, HN(CH,), Bre ret 1 equivalent ss cr + —s CH, or “OH Ho Hye [10 marks]Chemistry 230 Final Examination Semester 01-2004 Page 4 of 6 8. Explain the product ratios shown below. A few sentences may provide the best answer to this question, An abbreviated curved arrow mechanism may help but it is not required CH. whl Moi CH; @ to, + Br CH 98% 05% [3 marks] Br H3C._0. Bry H3C._0. Br H3C._0. wo oO. paid qf CL » Chapaeegen) ‘CH, ‘CHy minor product major product (3 marks} 9, In regard to the two molecules shown below: | CH, @ tc=n> (ii) HgC-O-CHy | cH, (a) Indicate the hybridization of the carbon, oxygen and nitrogen atoms highlighted in the molecules. (b) What is the shape (with reasoning) of the molecule around the nitrogen atom? [4 marks]Chemistry 230 Final Examination ‘Semester 01-2004 Page 5 of 6 10. Draw the curved arrow mechanism to show the formation of the major product and the two minor products as indicated below. CH HBr sre 4. two other brominated minor products 95% [4 marks] 11. Rank the following species according to the stated criteria (a) Stability of the carbocation cH,9 cH, CHs —CH3 (CHg -=CH, HC: CH; CH3 CH3, (b) Rate of aromatic electrophilic substitution ae S OH 6 F (©) Stability of the carbanion ‘Ce co or (d) Relative stability of the alkene Hye OH Ha aed Hye CHy [4 marks]Chemistry 230 Final Examination Semester 01-2004 Page 6 of 6 12. For each reaction assign the most likely mechanistic route, ie., Sy1, Sx2, El or E2. ° Cl OP 20 9 Y Y (a) + Hot o —> CH; + CH; Hs bus bus cl a ) + Hef Pe ds CHs CHg (©) He—-or + HNN ScHy = CH, (4) Br cHy + H3c-o° — [4 marks] +44 End of Examination ****###*shee oe, cel BER: Sfce sg 1 potassiom 29-1 7 Rb rutin 55 Cs 132-6 Fr franca Be berlin 9-0 2 Mg magnesium 263 20 2 2 Ca Se Ti calcium seandiun ——_tanum 40-1 45-0 479 38 29 40 Sr Y 2r stontium yttrium zirconium 876 88:9 12 56 57 72 Ba La Hi barium fanthanum hafnium 1373 138-8 178-5 28 89 Ra Ac radu actium, 58 59 Ce Pr ccefiun Praseodymiu » a Th Pa thedun Protoactinium Fa v vanacum 50:8 4 Nb sicbiurn, 92-8 mB Ta tantalum 180-S 60 ‘neodymium » * PERIODIC TABLE OF THE ELEMENTS 2 2 26 2 Cr Mn Fe Co vom manganese kon expat 320 m3 se se9 42 8 “4 45 Mo Te Ru Rh rmetyedenum technetium — ruherium ——thoium 5-0 389 “ort 1028 7 7s 76 7 w Re Os ir fungsten thera =i iidum wees “te? 02 TORR a «2 e Pm sm Eu promethium samarium = europium 9 Pa 95 Np Pu Am ‘Reptunium Plutonium americium platiourn 1951 Gd ‘gadolinium cm ceriuen berkelium 5 6 B c boron carbon 108 120 8 “4 A Si aurinium ——alcon 20 2:1 20 1 2 Zn Ga Ge Ze gaius ——_germanium 4 0-7 72-6 48 49 0 Cd In Sn czcrium num tn Wea 8118-7 e0 a 2 Hg rf Pb mercury thalium lead 200-6 = 2k 207-2 67 Dy Ho @ysprosium = talnium 2 Es cattorium ——_ebstenium ritrogen 14-0 Er erbium 100 fermium VI tet Cy Tm thsium 101 ‘mendetevium He bliam 40 8 to F Ne ‘uotine ‘neon 19-0 20-2 7 6 cl Ar chlorine ‘argon 35°5 38-9 3s 6 Br Kr bromine —_ypion 79:8 8 a Xe 133 8s a6 At Rn astatine radon 1 Yb yiertiue, 12 No oben m Lu utetian 103 arena