重要有機反應機理ppt課件-資料下載頁

　　

【正文】 H +C H 3 C 6 H 5C H 3H 3 CC C H 3H 3 C+C=C H 2C 6 H 5C H 3 C H2CH 3 C C H 3H 3 C C 6 H 5++H 3 C C H 3C 6 H 5C H 3HH +思考題： 例題： 2,3二氯丁烷在叔丁醇鈉的叔丁醇溶液中進行消除反應，得到兩個順反異構體，分別寫出其反應歷程。 【 解 】 2,3二氯丁烷有兩個手性碳原子，故有三個旋光異構體，即一對對映體和一個內消旋體。 C H 3C H 3HHC lC l C lC lHHC H 3C H 3C H 3C H 3HHC lC lO C ( C H 3 ) 3( C H 3 ) 3 C O H CCC H 3C H 3HC l+ C lC H 3C H 3HHC lC l C H3C H 3HHC lC lO C ( C H 3 ) 3( C H 3 ) 3 C O H CCC H 3C H 3HC l+ C l一對對映體 內消旋體 C H 3H O C H 2 C H 3HH + C H 3C H 2 C H 3C H 3H O C H 2 C H 3HH + C H 3C H 2 C H 3H +C H 3H 2 O C H 2 C H 3H + H 2 OC H 3 C H2 C H 3H +C H 3 C H 2 C H 3H+O HH +1 .2 . C ( C H 3 ) 2O HH + C H 3C H 33 .C H 3C H 3DHHB rC 2 H 5 O N aC 2 H 5 O H C = CC H 3C H 3HHO HH +1 .2 . C ( C H 3 ) 2O HH + C H 3C H 33 .C HC H 3DHHB rC 2 H 5 O N aC 2 H 5 O H C = CC H 3C H 3HHO HH +1 .2 . C ( C H 3 ) 2O HH + C H 3C H 33 .C H 3C H 3DHHB rC 2 H 5 O N aC 2 H 5 O H C = CC H 3C H 3HHC H 3H O C H 2 C H 3HH + C H 3C H 2 C H 3H +C H 3H 2 O C H 2 C H 3H+ H 2 OC H 3 C H2 C H 3H +C H 3 C H 2 C H 3H+思考題 C H 2 C H 2 C H 2 C H OO H+ C H 3 C H 2 O H干 H C l OO C H 2 C H 3C=OHO HH + C=O HHO H+： O HO HH+：OO H 2H+H 2 OOH+H O C 2 H 5：OO C H 2 C H 3H+HH+OO C H 2 C H 32 .==OOC H 3 + C H 3 C C H = C H 2=OC 2 H 5 O N aC 2 H 5 O H == OOH 3 C==OOC H 3C 2 H 5 O N aαC 2 H 5 O H==OOC H 3=O=O=O OC H 3C H 3C 2 H 5 O H=O=O O HC H 3C H 3重 排 =O=O OC H 3C H 3=O H=O=O OC H 3C H 2==OC H 3O=O=OC H 3O=H OC 2 H 5 O H H 2 O=OC H 3O===OOC H 3C 2 H 5 O N aαC 2 H 5 O H==OOC H 3=O=O=O OC H 3C H 3C 2 H 5 O H=O=O O HC H 3C H 3重 排 =O=O OC H 3C H 3=O H=O=O OC H 3C H 2= 思考題： 1 . 2 C H3C H2C H Od i l . O H△C H3C H2C H = C C H OC H32 .=O+ C H3C C H = C H2=OC2H5O N aC2H5O H=OHO H=OC2H5O N aC2H5O H=O3 .C H 2 ( C O 2 E t ) 2 E t O N aE t O HOOOC O 2 E t4 .O H H + + +O H H +H C lC lH N O 2H N O 2N H 2O HC H 2 N H 2O H OC H OHNO HH2S O41 1 0 ℃HHNH OH2S O41 1 0 ℃HHNHHON HHHO例 3N H N HH 2 N N H 2 N H 2+O M e M e ON H N HO E t E t OM e O O M eH 2 NE t O O E t+H +例 3N H N HH 2 N N H 2 N H 2+O M e M e ON H N HO E t E t OM e O O M eH 2 NE t O O E t+H +K O HM eC O C H 3C lHH OM eHOH +M eHC H 2OO HM eHM eC O O HK O HM eC O C H 3C lH H+M eHC H 2 OO HM eHM eC O O HH2O 注意開環方向 —— 穩定的負離子 O H C COOC CO O HO CO HO O CO H OOR O HN a O RP h C C P hOO H 3 O +P h2 CC O O RO P h 2 CC O O RO HR CONHO HR N H 2 + C O 2 + H 2 O加 熱 H 2 O或 S O C l 2( C H 3 C O ) 2 O , P 2 O 5異 羥 肟 酸R O HN a O RP h C C P hOO O HC COO？ ？ P hP hO O RO2022中科大 2022 試為下列反應提出合理的反應機理： +HO HRRRROH C lC l++HH B rC H 3 O HC H 3C H = C H 2C H 3 C = C H C H 2 C H 2 CB r++HO HC H 3 RO HC H 3RRC H 3OR RO ORRORRH+++++H HH O H O HRRRRHC lC l++H++ H++ H+++H1 2 OH 3 CRRC H 3O HRC H 3O HH+ROHRO+H +O HRH OC H 3R++++H ORRH O+C H 3 RO HHH++H 3 CH 3 CH 3 CH 3 CH 3 CC H 3 C = C H C H 2 C H 2 C C H = C H 2C H 3O HC H 3C H 3 C = C H C H 2 C H 2 C C H = C H 2C H 3O H 2C H 3C H 3 C = C H C H 2 C H 2 C C H = C H 2C H 3C H 3C H 3 C = C H C H 2 C H 2 C C H C H 2C H 3H 2 OC H 3 ++++B rB rH+ HB rHB r例 解釋下列事實： （ 1）赤式 3溴 2丁醇 內消旋 2,3二溴丁烷 +..M eHM eB rHM eB rH+M eB rHM eB rHM eB rH+M eB rHH H 2 O+M eB rHM eM eB rHM eB rHHO H 2M eB rHH OHB rM eO HM eHHM eB rHO HM e+..M eHM eB rHM eB rH+M eB rHM eB rHM eB rH+M eB rHH H 2 O+M eB rHM eM eB rHM eB rHHO H 2M eB rHH OHB rM eO HM e HB rB rHM eHM e1 2 （ 2）蘇式 3溴 2丁醇 外消旋 2,3二溴丁烷 + C H C l 3C H OO HH 2 ON a O HO H+ B r 2C H 3 O / C H 3 O HOO C H 3NHN H 2O C l..C lC H C lOC C l 2HOC C l 2OO HO H..__ C lH 2 OC H 3 C l + O H C l 2 C C l C l 2 CO O HC H O.. +O H C lO HC HO HC H C lOC H C lON C O HO C H 3HH...... ++ON H C O C H 3O C H 3O HN C H O C H 3H O C H 3N C ONOO C H 3HB rNOB r B rN HOO C H 3HHNO07科 烯醇負離子動力和熱力 氧鹽 C+親電加 氧鹽 C+重排 06科 05科 鄰參與 溴鎓離子 Hoffman DA，逆 DA Dazens反應 [3,3]遷移，互變異構 04科 3 .2 .S OH 2 N C H 2 C H 2NH SOHOR RH 3 + OO HRR1 .N ( C H 3 ) C H 2 C H 2 N H C H 3N a N H 2E t 2 ONNC H 3C H 3C l3 .2 .S OH 2 N C H 2 C H 2NH SOHOR RH 3 + OO HRR浙大 3 .OO OC l＋ K O HOO1 . 2 .OH + OHC H 2 C O 2 E tC H 2 C O 2 E tO1 .2 .t B u O KH 3 O +＋ C O 2 E tC H 2 C O 2 H珜鹽羰基 C+ 氧負離子