中原大学九十学年度硕士班入学招生考试.docVIP

中原大學九十學年度碩士班入學招生考試 4月28日　　第2節 　　　　化學系 誠實是我們珍視的美德，我們喜愛「拒絕作弊，堅守正直」的你！ 科目： 有 機 化 學 （共4頁 第1頁） I. Supply the missing compounds in the following equations. Show stereochemistry where appropriate. If more than one organic product results, give only the major product. (34%) (a) (b) (c) (d) (e) (f) (g) (h) (i) (j) (k) (l) (m) (n) II. Synthesis： (20%) 1. Trans-2-penene from HC≡CH ? 2. ? 3. from alcohols of three carbons. 4. and any other reagents. III. Give a mechanism for the following： (12%) 1. R2C＝N─NH2 + HO-→ R2CH2 + N2 2. CH3CH＝CH2 + HBr CH3CH2CH2Br IV. Answer the following question： (16%) 1. Arrange the following compounds in order of decreasing heat of hydrogenation.  2. List the following compounds in order of decreasing reactivity toward CH3O- in an SN2 reaction carried out in CH3OH : CH3F, CH3Cl, CH3Br, CH3I, CH3OSO2CF3, 14CH3OH. 3. Arrange the following in order of reactivity toward acid-catalyzed dehydration: 1-pentanol, 2-methyl-2butanol, 3-methyl-2-butanol V. Spectroscopy: (10%) Give a structure consistent with each of the following sets o proton NMR data: (a) C10H12 a. multiplet δ0.65, 2H b. multiplet δ0.81, 2H c. singlet δ1.37, 3H d. singlet δ7.17, 5H (b) C4H7BrO2 a. triplet δ1.30, 3H b. singlet δ 3.77, 2H c. quartet δ4.23, 2H (8%) (a) On catalytic hydrogenation, compound A, C5H8, gave cis-1, 2-dimethylcyclopropane. On this basis, three isomeric structures were considered possible for A. What were they? (b) Absence of infrared absorption at 890 cm- made one of the structures unlikely. Which one was it? (c) The NMR spectrum of A showed signals at δ2.22 and δ1.04 with intensity ratio 3:1. Which of the three structures in (a)is consistent with this? (d) The base peak in he mass spectrum was found at m/e 67. What ion was this peak probably due to, and how do you account for its abundance? 　　　　　--- END---