Organic Chemistry Exam(B)with Solution Midsemester Chinese Name: Student ID: Credit: 1.Name the following compounds in English (IUPAC)(20) (4R.6S)-4.6-dimethyl-3-octanone cyclohexanecarbaldehyde propyl propionate N,3-dimethylbutanamide 4-chloro-2-methylphenol (6)Br Ho-co,H 3-bromo-4-hydroxybenzoic acid (S)-4-methyl-2-hexynoic acid (8)coc trans-4-methylcyclohexanecarbonyl chloride methyl(1R.3R)-3-chlorocyclopentanecarboxylate (10) (2S.5R)-2-bromo-5-chloro-4-oxohexanal 2.Predict major products for following reactions and indicate the stereochemistry if optional.(20) 1 1.EtMgBr Ph 2.NH CI,H2O Ph 2. HONH2HCI HO-N +HcHO+ENH HCI△ NH
1 Organic Chemistry Exam (B) with Solution Midsemester Chinese Name: Student ID: Credit: _______________________________________________________________________________ 1. Name the following compounds in English (IUPAC) (20) (1) (2) CHO Cl Br (3) (4) (5) (6) (7) (8) (9) (10) CHO O H N CO2H COCl H CO2Me Cl H O O O Cl OH HO CO2H Br O (4R,6S)-4,6-dimethyl-3-octanone cyclohexanecarbaldehyde propyl propionate N,3-dimethylbutanamide 4-chloro-2-methylphenol 3-bromo-4-hydroxybenzoic acid (S)-4-methyl-2-hexynoic acid t rans-4-methylcyclohexanecarbonyl chloride methyl (1R,3R)-3-chlorocyclopentanecarboxylate (2S,5R)-2-bromo-5-chloro-4-oxohexanal 2. Predict major products for following reactions and indicate the stereochemistry if optional. (20) 1. EtMgBr 2. NH4Cl, H2O 1. 2. O Ο 3. + HCHO + Et2NH HCl 4. 5. Ph O + Ph3P+CH2Ph Cl- NaOH NH2 H O NaOH Br2 Ph O HONH2 HCl Ph HO (+) N HO Ο N (+) Ph Ph NH2 H
OH P(Cat.) 1)Mg,EtOEt (+) 3H6 10. 3. (1)Compound A(CoHO):'H NMR:8(ppm)1.25(t3H),2.57(s,3H),2.70(q.H),7.20 (d,2H),7.70(d,2H).A will produce 1,4-benzenedicarboxylic acid under the oxidation with KMnO.Please predict the structure of compound A. O O 0人 (4)Compound D (CHO)is a thermal stable compound.Its C NMR data:824.26.41. 212ppm.Compound D(CH)reacted with NaBHto produce con ound E.which compound under reuxing in the presence of sulfuric acid.Compound (CH):C NMR:2,24.5,126 ppm.Please predict the structures of compounds D and F. D
2 6. 7. 8. 9. 10. OH O P (Cat.) Br2 O 1) Bu2CuLi 2) EtI O HCO3H PhCH2Cl 1) Mg, EtOEt 2) CO2 3) H3O+ CO2H 1) SOCl2 2) AcOH O O OH O Br (+) O (+) PhCH2CO2H O O O 3. Identify the stereochemical relationships of the following structures (20) (1) Compound A (C10H12O): 1 H NMR: δ (ppm) 1.25 (t, 3H), 2.57 (s, 3H), 2.70 (q, 2H), 7.20 (d, 2H), 7.70 (d, 2H). A will produce 1,4-benzenedicarboxylic acid under the oxidation with KMnO4. Please predict the structure of compound A. O (2) Compound B (C8H10): 1 H NMR: δ (ppm) 1.20 (t, 3H), 2.64 (q, 2H), 7.10-7.30 (m, 5H). Please predict the structure of compound B. (3) Compound C (C3H6O): 1 H NMR: δ (ppm) 1.10 (t, 3H), 2.47 (dq, 2H), 9.78 (t, 1H). Please predict the structure of compound C. O (4) Compound D (C6H10O) is a thermal stable compound. Its 13C NMR data: δ 24, 26, 41, 212 ppm. Compound D (C6H12O) reacted with NaBH4 to produce compound E, which generated compound F under refluxing in the presence of sulfuric acid. Compound F (C6H10): 13C NMR: δ 22, 24.5, 126 ppm. Please predict the structures of compounds D and F. O D F
4.Write stepwise and reasonable mechanisms for the following reactions(20) moc入人CHO MOH0 NapH H、H20 8>eo一co= 7告0 回er、edanet mo aner rm2g女o m0ws心8.鸣e o dgr "sO8oO招一Og "○ 5.Synthesize the following organic compounds with provided starting materials and necessary Srting Bencne.Toluene (MCH phalene.CH-CHCOMe.ECO Ac20. 1)
3 4. Write stepwise and reasonable mechanisms for the following reactions (20). (1) OHC CHO NaOH CHO (2) RC H+ R+C=NH O (3) O O MeOH, 100 oC O CO2H O (4) CHO OH TsOH O OHC CHO NaOH H O CHO - CHO -H2O O- H2O -OHCHO OH H OH- -H2O CHO N H2O R OH2 + NH H+ transfer R OH NH2 + H2O R OH2 + H2N OH H+ transfer R OH +H3N OH -NH3 R OH OH+ -H+ RCO2H O O O- OMe H+ H+ transfer O O O- OMe H+ CH=OH+ HOCH2CH2OH OH H+ H+ transfer OH O OH2 + HO -H2O O+ O O H+ -H+ O O 5. Synthesize the following organic compounds with provided starting materials and necessary inorganic reagents. (20) Starting materials: Benzene, Toluene (MeC6H5), naphthalene, CH2=CHCOMe, EtCO2H, Ac2O. O Ph (1) O Br (2) Cl CO2H (3) (4) O
(O.NG NOH CH-CHCOve o noro 04“OpmC 0力
4 O Ph O Br (2) (3) O (4) Ac2O, AlCl3 (1) O NaOH CH2=CHCOMe O O NaOH Br2, FeBr3 Br AlCl3 Cl O Cl CO2H Cl O Cl O SOCl2 Cl Cl2, FeCl3 H2SO4 HO3S HO3S Cl H3O+ KMnO4, H+ H2, Ni Br2, hv Br NaOH 1. O3 2. Zn, HOAc O O NaOH
