脂肪胺的碱性气相下:RN>R2NH>RNH>NH水溶液:R,NH>RNH,>R3N>NH3CH3NH2(CH3)2NH(CH3)3NpKp3.233.364.26CH.NH2(C,Hs)2NH(C2Hs)3NpKp3.333.073.42
脂肪胺的碱性 C2H5NH2 (C2H5 )2NH (C2H5 )3N pKb 3.33 3.07 3.42 CH3NH2 (CH3 )2NH (CH3 )3N pKb 3.36 3.23 4.26 气相下: R3N>R2NH>RNH2>NH3 水溶液: R2NH>RNH2>R3N>NH3
溶剂化作用OH2H---.OH2H---.OH2-H-----OH2R----.OH2H.H---.OH2芳香胺的碱性NH3NH2NH >(
溶剂化作用 R +N H H H OH2 OH2 OH2 > R N R + H H OH2 OH2 > +N R R R H OH2 芳香胺的碱性 NH3 > NH2 > ( ) NH > 2 ( )3 N
13.2.3.2 AcidityFe3+HNa+CHNH2CHNHNa[(CH3)2CH]2NH + n-CH,Li → [(CH3)2CH]2NLit + n-CH10
13.2.3.2 Acidity Na CH3NH2 Fe 3+ CH3 -NHNa + 1 2 H2 [(CH3)2CH]2NH [(CH3)2CH]2NLi+ n-C4H9Li n-C4H10
13.2.3.3 Alkylation13.2.3.3.1N-alkylationH20t-BuNH,t-BuNHCH,CH,OH +t-BuN(CH,CH2OH)2NH3(过量)+CH2CH一CNH,NCH,CH,CN+HN(CH2CH2CN)231~33%57%NH3+CH3→CH3*NHI+(CH3)2+NH,I+(CH3)3NHI +(CH3)4+NI
13.2.3.3 Alkylation 13.2.3.3.1 N-alkylation NH3 (过量) CH2 CH CN H2NCH2CH2CN HN(CH2CH2CN)2 31~33% 57% NH3 CH3I CH3 +NH3I - (CH3)2 +NH2I - (CH3)3 +NHI - (CH3)4 +NI - O H2O t-BuNH2 t-BuNHCH2CH2OH t-BuN(CH2CH2OH)2
CH3COOCH3CH3CH3NH2+CH3CHOSO2CH3NHCHCOOCH3+CH3SO.HCHCH3R'催化剂H20RNH, + R'CR" +H2RNHCH十R
CH3 NH2 CH3 CH3CH COOCH3 OSO2 CH3 CH3 NHCHCOOCH3 CH3 CH3 CH3 SO3H RNH2 R'C O R'' H2 催化剂 RNHCH R' R'' H2O