第十五章 有机含氮化合物
(一) 写出下列化合物的构造式或命名:
(1) 仲丁胺 (2) 1,3-丙二胺 (3) 溴化四正丁铵 (4) 对氨基-N,N-二甲苯胺 (5) (CH3)2NCH2CH2OH (6) H2NNHCH2CH3 (7)
(CH3)3NCHCH2CH2CH2NH2+OH -
(8) H2NCH2CH2CH2NH2 (9)
解:(1)
CH3CH2CHCH3NH2 (2) H2NCH2CH2CH2NH2
+-(3) (CH3CH2CH2CH2)4NBr (4) H2NN(CH3)2
(5) 2-二甲氨基乙醇 (6) N-苄基对苯二胺 (7) 氢氧化三甲基(1-甲基-2-苯基乙基)铵 (8) 2-对氨甲基苯基乙胺 (9) 2-(α-萘基)乙胺
(二) 两种异构体(A)和(B),分子式都是C7H6N2O4,用发烟硝酸分别使它们硝化,得到同样产物。把(A)和(B)分别氧化得到两种酸,它们分别与碱石灰加热,得到同样产物为 C6H4N2O4,后者用Na2S还原,则得间硝基苯胺。写出(A)和(B)的构造式及各步反应式。
CH3解:(A)
NO2NO2CH3 (B) O2NNO2
(三) 完成下列转变:
(1) 丙烯异丙胺 (2) 正丁醇正戊胺和正丙胺
3,5-二溴苯甲胺 (4) 乙烯1,4-丁二胺 (3) 3,5-二溴苯甲酸 (5) 乙醇,异丙醇乙基异丙基胺 (6) 苯,乙醇α-乙氨基乙苯 解:(1)
BrCH3CH=CH2HBrNH2NH3CH3CHCH3CH3CHCH3
(2) 制正戊胺: NaCNCH3CH2CH2CH2OHH2NiPBr3CH3CH2CH2CH2Br
CH3CH2CH2CH2CNCH3CH2CH2CH2OHCH3CH2CH2CH2CH2NH2CH3CH2CH2COOHNaCr2O7NH3制正丙胺:
?
CH3CH2CH2CONH2NaOBr , OH-CH3CH2CH2NH2
COOH(3)
NH3CONH2NaOBr , OH-NH2
Br(4)
?BrCl2CCl4BrNaCNBrBr2H2BrCH2=CH2CH2CH2ClClCH2CH2NiCNCNH2NCH2(CH2)2CH2NH2
(5) CH3CH2OH (CH3)2CHOH(6) CH3CH2OHPBr3CH3CH2BrNH3CH3CH2NH2
H2 , NiCrO3吡啶PBr3(CH3)2C=OCH3CH2BrAlCl3CH3CH2NH2NH3CH3CH2NHCH(CH3)2
CH3CH2NH2
O
+CH3CClCCH3CH3CH2NH2OH2 , NiCHCH3NHCH2CH3
(四) 把下列各组化合物的碱性由强到弱排列成序:
(1) (A) CH3CH2CH2NH2 (B)
CH3CHCH2NH2OH (C)
CH2CH2CH2NH2OH
(2 ) (A) CH3CH2CH2NH2 (B) CH3SCH2CH2NH2
(C) CH3OCH2CH2NH2 (D) NCCH2CH2NH2 (3 ) (A)
(C)
NHCOCH3 (B) NHCH3 (D)
NHSO2CH3
NCH3
解:(1) (A)>(C)>(B) (2) (A)>(B)>(D)>(C) (3)(D) >(C) >(A) >(B)
(五) 试拟一个分离环己基甲酸、三丁胺和苯酚的方法。
解:
(n-C4H9)3NOHCOOH(1) 5%Na2CO3(2) 分液有机层(1) 5%NaOH(2) 分液有机层水层COOHH+(n-C4H9)3N
OH水层H+(六) 用化学方法区别下列各组化合物:
(1) (A) (2) (A)
(C)
NH (B)
NH2 (C)
N(CH3)2
CH2CH2NH2 (B) CH2NHCH3
CH2N(CH3)2 (D) 对甲基苯胺 (E) N,N-二甲苯胺
(3) (A) 硝基苯 (B) 苯胺 (C) N-甲基苯胺 (D) N,N- 二甲苯胺 解:
NH(1)
NSO2CH3SO2ClCH3不溶固体NH2N(CH3)2NaOH,H2ONSO2Na+无反应CH3清亮溶液
CH2CH2NH2CH2NHCH3(2)
CH2N(CH3)2CH3NNH2CH3CH3Br2H2Oxxx清亮溶液p-CH3C6H4SO2ClNaOH/H2O不溶固体无变化清亮溶液无变化
白色沉淀白色沉淀p-CH3C6H4SO2ClNaOH/H2ONO2NH2(3)
5%HClx溶解溶解溶解p-CH3C6H4SO2ClNaOH/H2O清亮溶液不溶固体无变化NHCH3NCH3CH3
(七) 试分别写出正丁胺、苯胺与下列化合物作用的反应式。
(1) 稀盐酸 (2) 稀硫酸 (3) 乙酸 (4) 稀NaOH溶液 (5) 乙酐 (6) 异丁酰氯 (7) 苯磺酰氯+KOH(水溶液) (8) 溴乙烷
(9) 过量的CH3I,然后加湿Ag2O (10) (9)的产物加强热
(11) CH3COCH3+H2+Ni (12) HONO (即NaNO2+HCl),0℃ (13)邻苯二甲酸酐 (14)氯乙酸钠 解:1、与正丁胺的反应产物:
(1) CH3CH2CH2CH2NH3Cl (2) CH3CH2CH2CH2NH3 HSO4 (3) CH3COO NH3CH2CH2CH2CH3 (4) (5)
x
OCH3CH2CH2CH2NHCCH3O (6)
OCH3CH2CH2CH2NHCCH(CH3)2
(7) CH3CH2CH2CH2NSOPh K+ (8) CH3CH2CH2CH2NHC2H5
CH3CH2CH=CH2
+ N(CH3)3 + H2ON2 + CH3CH2CH2CH2OH (11) CH3CH2CH2CH2NHCH(CH3)2 (12)
+ CH3CH2CH=CH2O(9) CH3CH2CH2CH2N(CH3)3 OH (10) (13)
CNHCH2CH2CH2CH3COOH (14) CH3CH2CH2CH2NHCH2COONa
2、与苯胺的反应产物:
+-+-(1) PhNH3Cl (2) PhNH3HSO4 (3) CH3COO- NH3Ph
(4)
x (5)
OPhNHCCH3 (6)
OPhNHCCH(CH3)2
O(7) PhNSOPh K+ (8) PhNHC2H5 (9) PhN(CH3)3 OH
(10) PhN(CH3)2 + CH3OH (11) PhNHCH(CH3)2 (12) PhN2 Cl-
CONHPh(13)
(14) PhNHCH2COONa
COOH(八) 写出下列反应的最终产物:
CH2ClNaCNLiAlH4(CH3CO)2O(1) (2)
NO2Fe, HCl 2HCHO, 2H2, NiNaNO2 , HCl
OC(3)
N NaC
H2O, HO-CH3(CH2)2CH=CH2(4)
HBrROOROOHN(CH3)2 , H2 , Ni 解:(1)
CH2CH2NHCOCH3 (2) (CH3)2NNO
(3) CH3(CH2)2CH2CH2NH2 (4)
N(CH3)2O
(九) 解释下列实验现象:
1mol (CH3CO)2O,K2CO3HOCH2CH2NHCOCH3K2CO3HOCH2CH2NH21mol (CH3CO)2O,HClCH3COOCH2CH2NH3Cl
解:在K2CO3存在的碱性条件下,氨基亲核性强,因此,氨基更容易被酰化。
在HCl存在的酸性条件下,氨基形成-NH3+Cl-,无亲核性,此时羟基更容易被酰化。 用K2CO3处理后,游离的氨基具有亲核性,可发生如下反应:
CH3COOCH2CH2NH3ClK2CO3CH3COCH2CH2NH2OCH3-NH2
OO- H+CH3-NHOOCH3CNHCH2CH2O-O H+CH3CNHCH2CH2OHO
(十) 由指定原料合成下列化合物(其它试剂任选)。
(1) 由3-甲基丁醇分别制备:(CH3)CHCH2CH2NH2,(CH3)2CHCH2CH2CH2NH2和(CH3)2CHCH2NH2
OH(2) 由苯合成
CCH2NH2 和 CH3CH3NNHN
(3) 由CH3CH2NH2和1,5-二溴戊烷合成
NOCH2CH3
解: (1)
CH3CH3CHCH2CH2OHPBr3CH3CH3CHCH2CH2BrNH3(CH3)2CHCH2CH2NH2
(TM)
CH3CH3CHCH2CH2BrCH3 CHCHCHCHOH322NaCN(CH3)2CH(CH2)2CNCH3H2/Ni(CH3)2CH(CH2)2CH2NH2
(TM)
Na2Cr2O7H2SO4CH3CHCH2COOHNH3?(CH3)2CHCH2CONH2
- NaOBr , OH(CH3)2CHCH2NH2 (TM)
O(2)
CH3COClAlCl3OHCCH3CNH2NiOHCCH2NH2 (TM) CH3CCH3HCNHNO3H2SO4NO2FeHClNH2NaNO2+HCl0~5 CoN2 Cl-
高鸿宾四版有机化学答案第十五章含氮
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