物理有机思考题

P118 2 关于化合物 A B 的讨论 H H H H AB 1 A 的酸性大于 B 2 A B 化合物都可形成正负离子 参考 1 Yoshida Z Shibata M Tetrahedron Lett 1983 24 4585 Yoshida Z Shibata M J Am Chem Soc 1984 106 6383 2 Nakasuji K Yoshida K J Am Chem Soc 1983 105 5136 MinskyA Meyers AY J Am Chem Soc 1983 105 3975 Jonsall G Ahlbeerg P J Am Chem Soc 1986 108 3819 3 已知下列化合物是很强的有机碱 试指出哪个 N 原子接受质子 什么原因是它具有较强的 碱性 NN N NN N Schwesinger R Angew Chem Int Ed engl 1987 26 1165 4 将化合物 A 溶解在 78 的 FSO3H NMR 测定有碳正离子生成 将该溶液升温至 100 再用碱处理产生 B C 描述这一反应过程 PhC OH CH3 C CH3 CHPh A Ph CH3 CH3 Ph CH3 CH3 B C Miller W G Pittman C U Jr J Org Chem 1974 39 1955 P129 1 判断下列物质的芳香性 Vogel E Angew Chem Int Ed Engl 1974 13 732 2 利用羰基氧与苯酚形成氢键 通过测定形成氢键的键能 可以定性的了解羰基氧的碱性 下列化合物与苯酚形成氢键的平衡常数如下 试排列化合物的碱性和芳香性顺序 Create PDF with GO2PDF for free if you wish to remove this line click here to buy Virtual PDF Printer O H O O H O O H O O H O C6H5C6H5 C6H5C6H5 C6H5C6H5 K 6 2 31 283 2 11 7 C6H5C6H5 Bostwick D Henneike H F J Am Chem Soc 1975 97 1505 P220 5 提出下列物质变成更稳定离子的途径 CH3 CH3 H3C CH3 CH3 H3C H3C 1 Yano K J Org Chem 1975 40 414 Deno N C Friedman N Hodge J D Houser J J J Am Chem Soc 1963 85 2995 3 2 Lillien I handloser L J Am Chem Soc 1971 93 1682 4 Barborak J C Schleyer P v R J Am Chem Soc 1970 92 3184 Ahlberg P Engdahi C Jonsall G J Am Chem Soc 1981 103 1583 Create PDF with GO2PDF for free if you wish to remove this line click here to buy Virtual PDF Printer 6 预计下列物质在超酸中的离子形式 HO OH CH2CH2Cl Cl CH2OH 1 2 3 4 5 6 Brookhart M Diaz A Winstein S J Am Chem Soc 1966 88 3135 Olah G Bollinger J M Cupass C A Lukas J J Am Chem Soc 1967 89 2692 Olah G PerterR D J Am Chem Soc 1970 92 7627 Olah G Liang G J Am Chem Soc 1975 97 2236 Olah G Liang G J Am Chem Soc 1971 93 6873 Olah G Liang G J Am Chem Soc 1971 93 6873 P394 3 已知在乙酸溶剂解时 A 比 B 快 104 描述其反应历程 Br A Br B Wilt J W Chenier PJ J Am Chem Soc 1968 90 7366 Cristol S J Nachtigall G W J Am Chem Soc 1968 90 7132 7133 4 解释在水解时 双环化合物 C 比单环化合物 D 快 107 N O C N O D Somayaji V Brown R S J Org Chem 1986 51 2676 Create PDF with GO2PDF for free if you wish to remove this line click here to buy Virtual PDF Printer 5 解释在水解时 双环化合物 E 比单环化合物 F 快 1015 O X CH3 X E F Briggs AJ Evans C M J Chem Soc Perkin Trans 2 1983 1637 Quin C B Wiseman J R J Am Chem Soc 1973 95 1342 6 解释在二氧六环的碱性溶液中水解 G 比 H 快 8300 倍 CHCO2CH3 O G CO2CH3 H Bowden K Last AM J Chem Soc Chem Commun 1970 1315 7 判断下列反应的主产物 CCH2CH2BrH3CC CH3 CH3 O K OC CH3 3 O CH2 CH3 CH3 I O CH3 CH3 J Baldwin J E Kruse L I J Chem Soc Chem Commun 1977 233 8 下列化合物在水解时反应哪个比较快 O ONO2 CH3 K O ONO2 CH3 L Evans C M Glenn R KirbyAJ J Am Chem Soc 1982 104 4706 9 下列化合物脱去乙氧基反应哪个较快 N NO2 NO2 OC2H5 NO2 NO2 OC2H5 N MN Bunnett J F Sekiguchi S J Am Chem Soc 1976 98 8407 10 比较下列各组化合物在乙酸中溶剂解的速率 Create PDF with GO2PDF for free if you wish to remove this line click here to buy Virtual PDF Printer 1 TsO H OTs Schleyer PR Watts W E Fort R C Jr et al J Am Chem Soc 1964 86 5679 2 OPNB C CH3 3 OPBN CH3 Peter E N Brown H C J Am Chem Soc 1975 97 2892 3 H C Br PhO2C H C Br CO2Ph Ree B R Martin J C J Am Chem Soc 1970 92 1660 4 CH2 OTsOTs Lawton R G J Am Chem Soc 1961 83 2399 11 描述下列反应的反应历程 1 OH NH2 NaNO2 HClO4 H2OHC H O Cherest M Felkin H Sicher J et al J Chem Soc 1965 2513 2 OH NH2 H3C 3C NaNO2 HClO4 H2O H3C 3CO Cherest M Felkin H Sicher J et al J Chem Soc 1965 2513 3 O Br H HOC H O Marin J C Bartlettl PD J Am Chem Soc 1957 79 2533 Create PDF with GO2PDF for free if you wish to remove this line click here to buy Virtual PDF Printer 4 N CH3 OH CH3CO 2O H N CH3 OCCH3 O Archer S Lewis T R Bell M R et al J Am Chem Soc 1961 83 2386 5 CCH2Br H2C OCH3 Ag O2CCF3 Na2CO3 H H2O O Hill AE Greenwood G Hoffmann