第十一部分雜環(huán)化合物教學(xué) ppt課件

1、 1分類(lèi)分類(lèi)OSNH四氫呋喃(醚類(lèi))四氫吡咯(仲胺)四氫噻吩(硫醚類(lèi))NH哌啶(仲胺)N吡啶六元雜環(huán)NN喹啉異喹啉稠雜環(huán)OSNH呋喃吡咯噻吩五元雜環(huán)12345NHOS鍵長(zhǎng)0.1383nm鍵長(zhǎng)0.1371nm鍵長(zhǎng)0.1429nm鍵長(zhǎng)0.1362nm鍵長(zhǎng)0.1361nm鍵長(zhǎng)0.1431nm鍵長(zhǎng)0.1741nm鍵長(zhǎng)0.1370nm鍵長(zhǎng)0.1423nmNOHSNZZ=N,O,SE親電試劑進(jìn)攻3,4-位ZEHZEH兩個(gè)共振式雜原子利用其孤對(duì)電子來(lái)穩(wěn)定正碳離子-H+ZEZZ=N,O,SE親電試劑進(jìn)攻2,5-位ZEHZEHZEH-H+ZENHCH3COONO2-100CNHNO251%OONO2CH3COO

2、NO2-5300C35%SSNO2CH3COONO200C60%NOHSSBr2/C2H5OH00CNHBrOBrBrBr2/00CBr2/CH3COOH00CBrBrBrOOSO2Cl2/(C2H5)2O00CNClCl2-400COClI2/H2O00CSIH氯化硫酰氯化硫酰是一種溫和的氯代試劑苯不能直接與碘反應(yīng)但噻吩可以，說(shuō)明其親電取代活性遠(yuǎn)遠(yuǎn)高于苯NHSONSO3NSO3溫和的磺化試劑NHSO3NOSO3NHClNHSO3HHClOSO3HSSO3HH2SO4室溫苯中含有少量噻吩可以用濃硫酸萃取除去H2OS+ H2SO4NHNHC-CH3O(CH3CO)2O1502000CSSC-CH

3、3O(CH3CO)2OSnCl4OOC-CH3O(CH3CO)2OBF3Z=N,O,SZCOOHZCOOHBrBr2CH3COOHZ=N,O,SZBrZBrCH3COONO2NO2ZZ=N,O,SEZEHGG為第二類(lèi)定位基G親電試劑進(jìn)攻2-位，則導(dǎo)致正碳離子直接與吸電子基團(tuán)相連，不穩(wěn)定。ZEHZEZEHGGG如果進(jìn)攻4-位，不僅其本身活性低，而且也不如進(jìn)攻5-位時(shí)產(chǎn)生的共振式多。ZEHZEZEHGGGZEHG進(jìn)攻5-位最有利。ZZ=N,O,SEZEHGG為第一類(lèi)定位基GZEHGZEHG親電試劑進(jìn)攻2-位，則導(dǎo)致正碳離子直接與推電子基團(tuán)相連，這樣正碳離子穩(wěn)定。ZEHZEZEHGGGZEHZEZE

4、HGGGZEHG親電試劑進(jìn)攻這兩個(gè)位置時(shí)則無(wú)此共振式。ZZBr2CH3COOHNO2NO2BrZZCH3COONO2BrBrO2NZZ=N,SEZEHGG為第二類(lèi)定位基GZEHZEHGGZEGZEHZEZEHGGGZEHG親電試劑進(jìn)攻3-位，則導(dǎo)致正碳離子直接與吸電子基團(tuán)相連，這樣的正碳離子不穩(wěn)定。只有進(jìn)攻4-位時(shí)方可避開(kāi)這種情況，所以，當(dāng)2-位為吸電子基團(tuán)時(shí)，后續(xù)基團(tuán)進(jìn)入4-位。ZZ=N,SEZEHZEHGG為第一類(lèi)定位基GZEHGGZEHZEZEHGGGZEHGZEGZEHG雖然親電試劑進(jìn)攻3-位和5-位均能產(chǎn)生正碳離子與推電子基團(tuán)相連的情況，但是，進(jìn)攻5-位時(shí)產(chǎn)生三個(gè)共振式，而且5-位的

5、反應(yīng)活性比3-位高。OOOO+OOOONOOO+HOOONNOOO+NOOORRSOOO不反應(yīng)H2O2SOSOOOOOOONHNHpKb=2.89pKb=13.6說(shuō)明吡咯N上的H具有酸性。NaNH2NNaNHNMgXRMgX-RHClOONNH+ONHKNKClOONNH+ONH+N NClNHN NNHNHCHCl3NaOHCHONHNH(NH4)2CO3COONH4高溫H3+ONHCOOHd. 吲哚、咔唑及噻吩的吲哚、咔唑及噻吩的Vilsmeier反響反響 NC6H13POCl3 / DMFClCH2CH2ClNC6H13CHONCH3DMF / POCl3NCH3CHOSSDMF / P

6、OCl3CH2Cl2 室溫SSCHOOOCHOZnOCr2O3H3+O多聚戊糖(C5H8O4)nOHOOHOHOHNHHOCH2C CCH2OH5000CNH3CH CH2HCHOCuCl/NH4ClCH3CH2CH2CH3 + 4S6000CSSCOOHHOOCHOOC(CH2)4COOHSOCl2NHOSNH3NH3H2OH2OH2SH2SR1-C-CH2CH2 -C-R2OOP2O5OR2R1P2S5SR2R1(NH4)2CO3NR2R1HN123456 NKNO3/HNO3/H2SO4/Fe3000C NNO222%N20%SO3/H2SO42300C 24 hr NSO3H71%NB

7、r23000C 24 hr NBr30%NENEHNHENHENENEHNEHNEHNENEHNEHNEHNClClNaOCH3NOCH3ClNClCl2NaNH2NNH2NH2NClClNaCNNCNClNXNu-加成NXNuNXNuNXNu電負(fù)性大的N原子剛好帶有負(fù)電，有效地幫助分擔(dān)加成產(chǎn)生的負(fù)電荷，對(duì)穩(wěn)定中間體負(fù)碳離子非常有好處，而且只有取代2-和4-位時(shí)才能出現(xiàn)這樣的情況。-X-NNu消除NCH3NaOCH3NCH2NCH2NCH2NCH2NCH3CH3CH3Br2H2SO4, 回流NCH3CH3CH3NCCNNCH3CH3CH3BrBrCuCN, DMF回流NHArCHO, n-C3

8、H7OH回流NNCCNArArArAr = N(CH3CO)2ONClOHCH3CH3N SOOCH3COBrCHONClOHCH3N SOOCH3COBr C. N-氧化吡啶的親氧化吡啶的親電取代反響電取代反響NaOCH3NCH3CH2CH3NCH3CHCH3ClCH2NCH3CHCH2CH3NCH3NaOCH3NCH2C-HONNH2O2NOHNO3H2SO4一般硝化條件即可NONO2PCl3NNO2還原 D. 側(cè)鏈的氧化反側(cè)鏈的氧化反響響NCH3CH2CH3KMnO4NCOOHCOOHH+NCH3KMnO4NCOOHH+異煙酰肼(雷米封)H2NNH2NCONHNH2NNCH3KMnO4N

9、COOHH+尼古丁煙酸NH3NCONH2NClCH3COOCH3SeO2OONClCH3COOCHO E. 復(fù)原反響及成鹽復(fù)原反響及成鹽NNH2PtH六氫吡啶(哌啶)NSO3NSO3溫和的磺化試劑NCrO3NCrO3溫和的氧化試劑，將醇氧化為醛。NRXNRXR-C-ClO+ ROHNNNR-C-OClR-C-ORONHCl+ROHNHClNHClNCH3CH3CH3NCH3CH3CH3COOC2H5C2H5OOC1. KOH2. CaOCH3CCH2COOC2H5OCH3CHONH3NCH3CH3CH3COOC2H5C2H5OOCHHNO3CH3CCH2COOC2H5OCH3CHOCH3COO

10、C2H5COCH3C=CHKnoevenagel反應(yīng)CH3CCH2COOC2H5ONH3CH3COOC2H5HC=CH2NCH3CCH2COOC2H5NH親核加成生成亞胺互變異構(gòu)轉(zhuǎn)化為烯胺C2H5OOCCH3NH2CH3CH3COOC2H5OCH3CH3CH3COOC2H5C2H5OOCHNH2OCH3CH3CH3COOC2H5C2H5OOCHOHNH2NCH3CH3CH3COOC2H5C2H5OOCHH-H2ONCH3CH3CH3COOC2H5C2H5OOCHNO3NCH3CH3CH31. KOH2. CaOOOCHOR1R2R1=H; CH3; Cl; Br; CH2ClR2=H; CH3

11、; ClCH3COCH2COOC2H5CH3COONH4OOR1R2NCOOC2H5C2H5OOCCH3CH3H源自乙酰乙酸乙酯源自乙酸銨源自原料中的-CHONHCH3CH3C2H5OOCCOOC2H5RN-OHOO20 mol %O2, CH3CN, 回流CH3CH3C2H5OOCCOOC2H5RN在CH3COOH/H2O體系中，以H2O2為氧化劑，在加熱回流條件下也可發(fā)生上述反應(yīng)。 喹啉喹啉 異喹啉異喹啉b.p. 243C; pKa=5.4 b.p. 238C; pKa=4.8NN1234567812345678 A. 親電取代反響親電取代反響NHNO3H2SO4NNO2+NNO2NBr2

12、NBr+NBrH2SO4NNSO3H-SO3H中的H+與吡啶的N中和生成分子內(nèi)鹽。NHO3S濃H2SO43000C生成穩(wěn)定的熱力學(xué)產(chǎn)物，相當(dāng)于對(duì)-氨基苯磺酸內(nèi)鹽。NClOHCH3HSO3ClNClOHCH3ClO2SNHNO3H2SO4NNO2NNBrBr2NNSO3HH2SO4NOHNOHCH2ClH-C-HO(37%)濃鹽酸及HCl氣體N親電試劑進(jìn)攻5,8-位ENHENHEN親電試劑進(jìn)攻6,7-位ENHENNaNH2NH3phNphNH2NphLiNphHLi帶負(fù)電的苯基對(duì)吡啶環(huán)的親核加成。H3+ONHphHNO2硝基苯作為氧化劑通過(guò)氧化恢復(fù)芳香環(huán)，本身被還原為苯胺。NphNC2H5MgB

13、rNHC2H5MgBrH3+ONHHC2H5NO2NC2H5NKMnO4H+NHOOCHOOC氧化活化的苯環(huán)NCOOHNKMnO4NHOONNH2CH2OHCH2OHCH-OH+NO2H2SO490%CH2OHCH2OHCH-OHH2SO4CH2=CHCHOSkraup成環(huán)反應(yīng)的原料之一為不飽和醛(酮)：R-CH=CH-CHO；R-C-CH=CH-RO(3) Michael加成產(chǎn)物烯醇化脫水成環(huán)；加成產(chǎn)物烯醇化脫水成環(huán)； NH2CH2=CH-C-HONHCH2CH=C-HOHNHCH2CH2C-HONHCH2CH2C-HONHHOHH-H2ONHNHNO2+NNH2+苯胺在此是循環(huán)使用的。NH2NGCH2OHCH2OHCH-OHH2SO4NO2G+G向氨基的兩個(gè)鄰位成環(huán)是等效的。NH2NGCH2OHCH2OHCH-OHH2SO4NO2G+G只能向氨基的另一個(gè)鄰位成環(huán)。NH2NGCH2OHCH2OHCH-OHH2SO4NO2G+GG是推電子基團(tuán)時(shí)，向該基團(tuán)對(duì)位成環(huán)為主產(chǎn)物。NH2NGCH2OHCH2OHCH-OHH2SO4NO2G+GG是吸電子基團(tuán)時(shí)，向該基團(tuán)對(duì)位鄰環(huán)為主產(chǎn)物。NH2R1-C-CH=CH-R2NO2O+N