第八章脂肪胺

1、 N sp3含孤对电子，是很好的亲核试剂。NHCH3C2H5NHCH3C2H5翻转活化能=2527kJ/mol通过烷基化反应将其固定phCH2ClNHCH3C2H5phCH2ClNHCH3C2H5phCH2Cl对映体关系10胺CH3NH2 甲胺 CH3-C-NH2 叔丁胺 环己胺CH3CH3NH2 H2NCH2CH2NH2 乙二胺NH2苯胺20胺CH3NHC2H5 甲乙胺 (C2H5)2NH 二乙胺 NH哌啶(六氢吡啶)H2NCH2CH2NHCH2CH2NHCH2CH2NH2 三乙烯四胺 (多乙烯多胺)NHCH3N-甲基苯胺30胺CH3NC2H5 C3H7 甲乙丙胺(C2H5)3N 三乙胺N(

2、CH3)2N,N-二甲基苯胺NNNN六次甲基四胺(乌洛托品)季铵盐(碱)(CH3)4NOH 氢氧化四甲基铵 C16H33N(CH3)3Br 十六烷基三甲基溴化铵(CTAB)O-P-OOOCOOCOO+Ndipalmitoyl phosphatidylcholine (DPPC) (双棕榈酰磷脂酰胆碱，红细胞磷脂) (CH3CH)2NH + n-C4H9LiCH3(CH3CH)2NLi + n-C4H10CH3胺的氢的酸性仅比烷烃氢的酸性强RNH2 + H+ RNH3+ SO2ClCH3RNH210胺与对-甲基苯磺酰氯反应SO2NHRCH3由于磺酸基吸电子使NHR中的H具有酸性溶于NaOH不溶于

3、HClSO2ClCH3R2NH20胺与对-甲基苯磺酰氯反应SO2NR2CH3由于无H原子可与NaOH和HCl反应，不溶于酸和碱不溶于NaOH不溶于HCl SO2ClCH3R3N30胺与对-甲基苯磺酰氯反应SO2NR3CH3生成离子性化合物可溶于水Cl溶于NaOH溶于HClLeuckart 反应C-CH3OH-C-ONH4O1850CCHCH3NH2Eschweiler-Clarke 反应CH2CH2NH2H-C-HO2HCOOHCH2CH2NCH3CH3CH3NHH-C-HOHCOOHCH3NCH3CH3NH2CH3COOOHCH3NOCH3NH2CH3COOOHCH3NOCH3NH2CF3C

4、OOOHCH3NO2CH3NH2CF3COOOHCH3NO2NH2MnO2OOK2Cr2O7NH2苯胺黑N-HH2O2N-OHN-羟基化合物(C2H5)3NH2O2(C2H5)3N ON-氧化物R3N + HNO2 R3NH NO2(CH3)2NNaNO2HCl(CH3)2NNOCH3NHNaNO2HClCH3-NNOSnCl2HClCH3NHRNH2NaNO2HClR-N=NCl生成重氮盐的机理：HON=O H2ON=OH+-H2ONORNH2RN-NOH2-H+RNH-N=OH+RNH-N=OH-H+RN=N-OH重氮酸H+RN=N-OH2-H2OR-N=NR-N2ph - C - C -

5、 CH3phCH3HONH2NaNO2HClCH3 - C - C - phphCH3ONaNO2HClHONH2HON=N-N2HOCH2OH-H+O(CH3)3SiOHNH2HH123NaNO2CH3COOH(CH3)3SiOHNHHN123a. C1-C2迁移b. C2-C3迁移-N2(CH3)3SiO13-H+-H+abOSi(CH3)313即(CH3)3SiO13OSi(CH3)313即58%42%CH3CH2CHCH3N(CH3)3OHCH3CH2CH=CH2 + CH3CH=CHCH3 主产物次产物CH3CH-CH-CH2N(CH3)3HHOHHO酸性强主产物CH3CH2CH=C

6、H2 HDHN(CH3)3OHHDHN(CH3)3OH+ HDO + (CH3)3NOHN苄基位的氢的酸性强N+ H2O+OHN联有吸电子基团的beta位的氢的酸性强+ H2OClCH2=CHCl+N OHNN+ H2OOH+ H2ONOOC2H5NOOC2H5OHphHD(CH3)3NphCH3HDCH3(CH3)3NphphHDCH3(CH3)3Nphph稳定构像上的反式消除OHphphCH3DCH3CH2CHCH3N(CH3)2H2O2CH3CH2CHCH3N(CH3)2O3级胺的氮氧化物CH3CH2CH=CH2 + 主产物次产物CH3CH=CHCH3 + (CH3)2NOH CH3CH

7、-CH-CH3N(CH3)2HOCH3CH2-CH-CH2(CH3)2NHO酸性强酸性弱主产物CH3CH2CH=CH2 HDHN(CH3)2+ (CH3)2NOHH2O2HDHN(CH3)2DOphHD(CH3)2NphCH3phHD(CH3)2NphCH3OH2O2HDCH3(CH3)2NphphOHDCH3(CH3)2NphphO稳定构像上的顺式消除phphCH3H-(CH3)2NOD CH3SO2ClCH3NH2CH3SO2NHCH3HNO2CH3SO2-N-CH3NOKOHC2H5OHCH3SO3C2H5+ H2O + CH2N2m.p. -1450Cb.p. -230CR-C-OHO

8、R-OHOHCH2N2R-C-OCH3OR-OCH3OCH3+ N2NNOOOCH3OHOHOCH3C4H9C N NH(CH3)3Si重氮甲烷的碳原子以正碳离子形式与-OH中氧原子的孤对电子结合，实现-OH的甲基化。CH2Cl2NNOOOCH3OCH3OCH3OCH3C4H965%C N NH(CH3)3Si重氮甲烷作为-OH的甲基化试剂与羧酸中的-OH反应要比与醇中的-OH反应更容易。OHOHOHNOOOHOCH3OHNOO95%R-C-HOCH2N2R-C-CH3O+ N2R1-C-R2OR1-C-CH2R2OR1-C-R2(H)OCH2-N=N(亲核加成)R1-C-R2(H)OCH2-N=NR1-C-CH2R2(H)O-N2OCH312ONONBF3OCH3F3BNC4H9COOCH3N3OC4H9COOCH3NF3BN对应的构象中正负电荷相邻稳定C2-C3处于N N的反式迁移12OCH3C4H9COOCH3379%412OCH3F3BNC4H9COOCH3N312OCH3F3BCOOCH3NC4H9N34C2-C4单键旋转ONC4H9F3BNOCH3O氧原子之间排斥不稳定C1-C2处于N N的反式迁移12OCH3COOCH3C4H93 CH2-N=NCH2=CH2CH2-N=NCH2 CH2NNHRCNR-C-NH2ORNO2H2PtRNH2RCH2N