有機(jī)化學(xué)學(xué)習(xí)筆記：第八章脂肪胺

1、 N sp3含孤對(duì)電子，是很好的親核試劑。NHCH3C2H5NHCH3C2H5翻轉(zhuǎn)活化能=2527kJ/mol通過烷基化反應(yīng)將其固定phCH2ClNHCH3C2H5phCH2ClNHCH3C2H5phCH2Cl對(duì)映體關(guān)系10胺CH3NH2 甲胺 CH3-C-NH2 叔丁胺 環(huán)己胺CH3CH3NH2 H2NCH2CH2NH2 乙二胺NH2苯胺20胺CH3NHC2H5 甲乙胺 (C2H5)2NH 二乙胺 NH哌啶(六氫吡啶)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(烏洛托品)季銨鹽(堿)(CH3)4NOH 氫氧化四甲基銨 C16H33N(CH3)3Br 十六烷基三甲基溴化銨(CTAB)O-P-OOOCOOCOO+Ndipalmitoyl phosphatidylcholine (DPPC) (雙棕櫚酰磷脂酰膽堿，紅細(xì)胞磷脂) (CH3CH)2NH + n-C4H9LiCH3(CH3CH)2NLi + n-C4H10CH3胺的氫的酸性僅比烷烴氫的酸性強(qiáng)RNH2 + H+ RNH3+ NH3 + CH3BrCH3NH2CH3BrCH3BrCH3Br(CH3)2NH(CH3)3N(CH3)4NBrNH2CH3I

3、NHCH3CH3IN(CH3)2NH2CH3OHH2SO4高溫高壓工業(yè)生產(chǎn)N,N-二甲基苯胺CH3C-ClOCH3NH2CH3C-NHCH3O(CH3CO)2OCH3COOHNH2NHCCH3OSO2ClCH3RNH210胺與對(duì)-甲基苯磺酰氯反應(yīng)SO2NHRCH3由于磺酸基吸電子使NHR中的H具有酸性溶于NaOH不溶于HClSO2ClCH3R2NH20胺與對(duì)-甲基苯磺酰氯反應(yīng)SO2NR2CH3由于無H原子可與NaOH和HCl反應(yīng)，不溶于酸和堿不溶于NaOH不溶于HClSO2ClCH3R3N30胺與對(duì)-甲基苯磺酰氯反應(yīng)SO2NR3CH3生成離子性化合物可溶于水Cl溶于NaOH溶于HClCH3NH

4、2CH3COOOHCH3NOCH3NH2CH3COOOHCH3NOCH3NH2CF3COOOHCH3NO2CH3NH2CF3COOOHCH3NO2NH2MnO2OOK2Cr2O7NH2苯胺黑N-HH2O2N-OHN-羥基化合物(C2H5)3NH2O2(C2H5)3N ON-氧化物R3N + HNO2 R3NH NO2(CH3)2NNaNO2HCl(CH3)2NNOCH3NHNaNO2HClCH3-NNOSnCl2HClCH3NHRNH2NaNO2HClR-N=NCl生成重氮鹽的機(jī)理：HON=O H2ON=OH+-H2ONORNH2RN-NOH2-H+RNH-N=OH+RNH-N=OH-H+RN

5、=N-OH重氮酸H+RN=N-OH2-H2OR-N=NR-N2ph - C - C - CH3phCH3HONH2NaNO2HClCH3 - C - C - phphCH3ONaNO2HClNH2OHCH3CH3NaNO2HClNH2OHCH3CH3OONaNO2HClNH2OHCH3CH3NaNO2HClNH2OHCH3CH3OONaNO2HClHONH2HON=N-N2HOCH2OH-H+OCH3CH2CHCH3N(CH3)3OHCH3CH2CH=CH2 + CH3CH=CHCH3 主產(chǎn)物次產(chǎn)物CH3CH-CH-CH2N(CH3)3HHOHHO酸性強(qiáng)主產(chǎn)物CH3CH2CH=CH2 HDHN

6、(CH3)3OHHDHN(CH3)3OH+ HDO + (CH3)3NOHN芐基位的氫的酸性強(qiáng)N+ H2O+OHN聯(lián)有吸電子基團(tuán)的beta位的氫的酸性強(qiáng)+ H2OClCH2=CHCl+N OHNN+ H2OOH+ H2ONOOC2H5NOOC2H5OHphHD(CH3)3NphCH3HDCH3(CH3)3NphphHDCH3(CH3)3Nphph穩(wěn)定構(gòu)像上的反式消除OHphphCH3DNN1. CH3I 2. Ag2ONNOHOHNN1. CH3I 2. Ag2ONNOHOH1. O3 2. Zn2 HCHO2 HCHOOOOOCH3CH2CHCH3N(CH3)2H2O2CH3CH2CHCH3

7、N(CH3)2O3級(jí)胺的氮氧化物CH3CH2CH=CH2 + 主產(chǎn)物次產(chǎn)物CH3CH=CHCH3 + (CH3)2NOH CH3CH-CH-CH3N(CH3)2HOCH3CH2-CH-CH2(CH3)2NHO酸性強(qiáng)酸性弱主產(chǎn)物CH3CH2CH=CH2 HDHN(CH3)2+ (CH3)2NOHH2O2HDHN(CH3)2DOphHD(CH3)2NphCH3phHD(CH3)2NphCH3OH2O2HDCH3(CH3)2NphphOHDCH3(CH3)2NphphO穩(wěn)定構(gòu)像上的順式消除phphCH3H-(CH3)2NOD CH3SO2ClCH3NH2CH3SO2NHCH3HNO2CH3SO2-N

8、-CH3NOKOHC2H5OHCH3SO3C2H5+ H2O + CH2N2m.p. -1450Cb.p. -230CR-C-OHOR-OHOHCH2N2R-C-OCH3OR-OCH3OCH3+ N2R-C-HOCH2N2R-C-CH3O+ N2R1-C-R2OR1-C-CH2R2OR1-C-R2(H)OCH2-N=N(親核加成)R1-C-R2(H)OCH2-N=NR1-C-CH2R2(H)O-N2 CH2-N=NOOCH2-N=NO63%OCH2-N=NO15%R-C-ClO2 CH2N2R-C-CH=N=NO-重氮酮Ag2OH2ORCH2-C-OHOAg2OROHRCH2-C-OROCOO

9、HHOOCNaN3H2SO4N=C=OO=C=NH2ONH2H2N CH2-N=NR-C-ClOR-C-OClCH2-N=NR-C-OCH2-N=N-Cl-CH2-N=NR-C-OCH-N=NC=C的形成N2的脫出R-的遷移同步完成O=C=C-R烯酮Ag2OH2ORCH2-C-OHOAg2OROHRCH2-C-OROCH2-N=NCH2=CH2CH2-N=NCH2 CH2NNHNNNRCH3CH2CHCH3BrNaN3CH3CH2CHCH3N3LiAlH4CH3CH2CHCH3NH2R-C-ClON3R-C-N-N=NOClO=C=N-R異腈酸酯H2ORNH2 + CO2 RX + NH3 R

10、NH2 R2NH R3N R4NXRXRXRXRX + NaN3 RN3 RNH2LiAlH4R-C-ClO1. NaN32. H2ORNH2 + CO2NH3RNH2OOONHOOK2CO3NKOO鄰苯二甲酸酐鄰苯二甲酰亞胺RX-KX親核取代NROOH3+OGabriel法OOO1. KOH2. Br(CH2)3BrN(CH2)3BrOOHNNHN(CH2)3OO(CH2)3NOONN50% NH2NH2NNH2N(CH2)3(CH2)3NH285 % NH2NH2.H2O / C2H5OH回流 6 小時(shí)OONH2NHNHOO+OOO-S-CH3OONKOODMF, 700C, 6 hOONOO Br2RNH2R-C-NH2ONaOHRCNR-C-NH2ORNO2H2PtRNH2RCH2NH2RCH2NH2CH=NCH3H2PtCH2NHLeuckart 反應(yīng)C-CH3OH-C-ONH4O1850CCHCH3NH2Eschweiler-Clarke 反應(yīng)CH2CH2NH