第17章有机含氮化合物 17-1 (1)B>A>C>D (2)C>A>B>D>E (3)D>A>B>C (4)C>B>A>D>E 17-2 (I)兴斯堡反应(2)a.FeCl3b.BrH0c.HNO2 17-3 (I)稀HCI(2)稀盐酸洗涤 17-4 ()CH2CN CH2CH2NH2 >CH2CH2NHCOCH3 CH2OH (2)HOCH2-C-NO2 CH2OH (3) ④CHcCH.CNCH.cocH, )cH-NGH方 CHE NTCOCH ()入CONH NH2 COONH COONH4 -COONH ⑧) o入入Na CH3 CH3CH3 CHs
17-1 (1) B> A> C> D (2) C >A> B> D> E (3) D>A>B>C (4) C>B> A>D>E 17-2 (1) (2) a . FeCl3 b. Br2/H2O c. HNO2 17-3 (1) HCl (2) 17-4 (1) CH2CN CH2CH2NH2 CH2CH2NHCOCH3 C CH2OH CH2OH HOCH2 NO2 (2) OCH3 Cl NO2 (3) CH2Cl (4) CH2CN CH2COCH3 CH3 N(CH3 )2 (5) CH3C NHCOCH3 (6) O (7) CONH2 COONH4 NH2 COONH4 N2Cl COONH4 Cl COONH4 N CH3 CH3 I N CH3 CH3 OH N(CH3 )2 (8)
OH 9Ho,s8asaHo,sN=N OH (10)NH. NO2 (11) NH-NO, (12)-CH=CH (13)CH.CH=CH2 Me2NCH2CH(Me)2 EtNMe2 17-5 (1)HOCH2CH2CI HOCH2CH2OCH2CH2OCH2CH2OH CICH2CH2OCH2CH2OCHCH2CI CH2OCH2CH2N(CH2COONa)2 CH2OCH2CH2N(CH2COONa)2 HCI (2)C/500℃ KOH/EtOH NMe (3) CH:COCI H2SO4 NHCOCH3 NH2 HS人NO2H©H0 人NH2
HO3S N2HSO4 (9) HO3S N N OH OH NH2 NO2 (10) NO2 NO2 (11) NH (12) CH CH2 EtNMe2 (13) CH3CH CH2 Me2NCH2CH(Me)2 17-5 HOCH2CH2Cl O HOCH2CH2OCH2CH2OCH2CH2OH ClCH2CH2OCH2CH2OCH2CH2Cl CH2OCH2CH2N(CH2COONa)2 CH2OCH2CH2N(CH2COONa)2 HCl (1) Cl2 (2) /500 KOH/EtOH NMe3 NO2 NH2 CH3COCl H2SO4 NHCOCH3 NO2 HO3S H /H2O NH2 NH2 (3)
17-6 HNO.SO.CH.CONH 低温 EOH、目标产物 NO, HSO NO2 NO2 NH2 NHCOCH NHCOCH3 NHCOCH3 2) Fe/HCI NHCOCH: 2CHOH/HS04、 △ 0、目标产物 △ NMe2 CH3 CH3 3 NO2 Fe/HCl CH3 NHCOCH3 H2SO4 CH.coci CH3 (对位产物分离出去) HNO3 NHCOCH3 CH H2SO4 NO2 NH低温 HHgo,人Jao,dNo,人 jc KCN/CuCN 目标产物 OH OH OH HNO NO2 (4) a.KOH CO2 b.H' H:So: COOH COOH OH QH Fe/HCL了 NH NH2 HOCH3 COOH COOCH3 (5 、CH3入OHiA4-目标化合物
17-6 CH3 (1) HNO3 CH3 NO2 Fe/HCl CH3 NH2 CH3COCl CH3 CH3CONH HNO3 CH3 CH3CONH NO2 H /H2O CH3 NH2 NO2 NaNO2 ✂✁ /H2SO4 CH3 N2 HSO NO2 4 EtOH ✄✆☎✂✝✂✞ H2SO4 /H2SO4 NO2 Fe/HCl NH2 CH3COCl NHCOCH3 HNO3 H2SO4 NHCOCH3 NO2 Fe/HCl NHCOCH3 NH2 2CH3OH/H2SO4 NHCOCH3 NMe2 H /H2O ✟✡✠☞☛✍✌ (2) CH3 HNO3 H2SO4 H /H2O CH3 NO2 ✎✑✏☞✒✔✓☞✕✗✖✗✘✚✙✜✛✣✢ Fe/HCl CH3 NH2 CH3COCl CH3 NHCOCH3 HNO3 H2SO4 CH3 NHCOCH3 NO2 CH3 NH2 NO2 NaNO2/HCl ✤☞✥ CH3 N2 NO2 Cl KCN/CuCN ✦★✧✓☞✕ (3) OH OH COOH HNO3 H2SO4 OH COOH NO2 Fe/HCl OH COOH NH2 HOCH3 H2SO4 OH COOCH3 NH2 (4) a. KOH b. H + CO2 (5) CH3 O HCN CH3 OH CN LiAlH4
COOH COCI CONH2 (6) a 17-7 OH CHs CH2CHCH2CH3 Mg/EtO ⊙OHCCH-CH-◇ ②H0 8公目标化合物 Et Et Et NO NH2 NHCOCH HNO3- CI-CHCHs NH2-CHCH3 H2S04 NO2 一NH、 光照NO入 令e目标物 NHCOCH NHCOCH3 OH NO2 NH2 CH(CH3)2 CH(CH3)2 CH(CH3)2 CH .Br (4) NO2 NO2 NH2 Br HNO, NH2 NHCOCH NH人CH,cOa OH NO2 NH- a.NaNO2 A 一目标物 b.H20 NHCOCH3
CH3 Cl (6) KMnO4 H2SO4 COOH Cl SOCl2 COCl Cl NH3 CONH2 Cl Br2 NaOH 17-7 CH3 (1) Cl2 CH2Cl Mg/Et2O OHCCH2CH3 CH2MgCl CH2CHCH2CH3 OH H2O NH3 Al2O3 EtBr AlCl3 Et HNO3 H2SO4 Et NO2 Fe HCl Et NH2 CH3COCl Et NHCOCH3 HNO3 H2SO4 Et NHCOCH3 NO2 Cl2 CHCH3 NHCOCH3 NO2 Cl NH3 CHCH3 NHCOCH3 NO2 NH2 Fe/HCl (2) (3) HNO3 H2SO4 Fe/HCl H2SO4 CH(CH3 )2 CH2CHCH3 OH CH(CH3 )2 NO2 CH(CH3 )2 NH2 Br2 /H2O CH3 HNO3 H2SO4 CH3 NO2 Br2 /Fe CH3 NO2 Br Fe/HCl CH3 NH2 Br NaNO2 HCl ✩✫✪ CH3 N2 Br Cl HNO3 H2SO4 Br Br2 /Fe Br NO2 NO2 NH2 NH2 NHCOCH3 OH NHCOCH3 A A ✬✮✭✫✯ ✰ 4 ✱ NH3 CH3COCl a. NaNO2 b. H2O
SO3H (5) △ ②H0 CHs NO,CH CH3 NH2 NHCOCH3 HNO3 NHCOCH3 NHCOCH3 NO2 Fe/HCI NaNO2 目标物 。HO-KCH NH2 N2CI 17-8 (1)设定：CH,OOCCH2 CHCOOCH,一RNH, 0 0 0 0 NH,R→HANHR HR 0 -OH 0 NHR NR一最终产物 OH OH NaNO, OH (2) CHNH,HC低温H,C H3 H0 H3C 17-9 A:CH2=CHCH2CH2NH2 B:CH:CH2CH2CH-NH2 C:CH2-CHCH-CH2N(CH D:CH2=CHCH-CH2 E888
CH3 H2SO4 CH3 SO3H ✲ ✳ NaOH✴☞✵ H2O CH3 OH H2SO4 HNO3 NO2 Fe/HCl NH2 CH3COCl NHCOCH3 H2SO4 HNO3 NHCOCH3 NO2 Fe/HCl NHCOCH3 NH2 NaNO2 HCl ✶✗✷ NHCOCH3 N2Cl HO CH3 ✸✺✹✗✻ ✼ 5 ✽ 17-8 : CH3OOCCH2CHCOOCH3 NH2 RNH2 O O O NH2R O O NH2R O O O NHR OH NHR O O OH NR O O 1 H2O NHR O OH OH ✾ 2 ✿ H3C OH CH2NH2 NaNO2 HCl ❀❂❁ H3C OH CH2N2 H3C OH CH2 ❃ N2 OH H3C O H3C ❃ H + 17-9 A: CH2=CHCH2CH2NH2 B: CH3CH2CH2CH2NH2 C: CH2=CHCH2CH2N(CH3 )3 D: CH2=CHCH=CH2 COOCH3 COOCH3 E: I