yy)Acylation and Sulfonylation Reaction 缚酸剂 除酸剂 R-C-CI or 0 RNh2 R-C-NHR′+ hCI or RCOOH R一C O Acylation R一C O O SO,CI RNH R-C-NHR HCI 苯磺酰氯 苯磺酰胺 Sulfonylation
(四) Acylation and Sulfonylation Reaction R C O Cl R C O R C O O or + R'NH2 R C O NHR' + HCl or RCOOH 缚酸剂 除酸剂 + R'NH2 R C O SO2Cl NHR' + HCl 苯磺酰氯 苯磺酰胺 Acylation Sulfonylation
Acylation and sulfonylation applications 药物合成中的应用 NE NH NHCOCH NHCOCH3 (CH3COhO (CH3CO)O OC OC2H5 OH 扑热息痛 非那西丁 (paraspen) (phenacetin) H2N SO2NH2 H2N SO2NHR 磺胺药(抗菌剂,利尿药,降糖药)
Acylation and Sulfonylation Applications 药物合成中的应用 NH2 OH (CH3CO) 2O NHCOCH3 OH (CH3CO) 2O NHCOCH3 OC2H5 NH2 OC2H5 扑热息痛 (paraspen) 非那西丁 (phenacetin) H2N SO2NHR 磺胺药 (抗菌剂，利尿药，降糖药) H2N SO2NH2
Acylation and sulfonylation O-N OO N N H H2N HN H2N 磺胺异口恶唑 磺胺嘧啶 磺胺地托辛 (Sulfafurazole) (Sulfadiazine) (Sulfadimethoxine) NH NH IN 乙酰唑胺( acetazolamide) 氢氯噻嗪( Hydrochlorothiazide) O N-C- NHCHCH NH-C. NH Me 格列美脲( Glimepiride)
S N O O O N H2N H S N O O H2N H N N S N O O H2N H N N O O 磺胺异 恶唑 (Sulfafurazole) 口 磺胺嘧啶 (Sulfadiazine) 磺胺地托辛 (Sulfadimethoxine) Acylation and Sulfonylation S NH2 O O N N N S O H S H2N O O S NH N O O H Cl 乙酰唑胺(Acetazolamide) 氢氯噻嗪(Hydrochlorothiazide) N O C O NHCH2CH2 S O O NH C NH O Me 格列美脲 (Glimepiride)
Acylation and sulfonylation 昴氨基的保护 NH, NHCOCH NHCOCH3 NH2 CH,CO HNO3/H2SO4 OH/H,O NO2 芳胺的易氧化性 乙酰氨基的定位规律 胺的分离、鉴定 Hinsberg reaction RNH, Na溶解 C6HSSO2NR C6HSSO2NR R2NH C6HsSO2CI NaoH(aq C6HSSO2NR2 CHsSO2NR2不溶 R3N R3N R3N不反应
氨基的保护 NH2 NH2 NO2 CH3COCl NHCOCH3 HNO3 /H2 SO4 NHCOCH3 NO2 OH- /H2 O 芳胺的易氧化性 乙酰氨基的定位规律 胺的分离、鉴定 Hinsberg Reaction RNH2 R2NH R3N C6H5 SO2Cl C6H5SO2NR H C6H5SO2NR2 R3N NaOH(aq.) C6H5SO2N - R Na + C6H5SO2NR2 R3N 溶解 不溶 不反应 Acylation and Sulfonylation
()Reaction with Nitrous Acid HNO2亚硝酸 NaNO2/HCl, NaNO2/H2SO4 芳香伯胺 重氮化反应 NH2 Diazotization Nano2/HCl(aq Nacl 0-5C Diazonium salt 氯化重氮苯 重氮盐 Mechanism HONO +h=HO-NO No + ho Ar-NH2 NO Ar-N-NO -Ar-N-N=0T Ar-N=N-OH H H Ar-N=N-OH H,O Ar-N三N
(五) Reaction with Nitrous Acid HNO2 , 亚硝酸 NaNO2 /HCl, NaNO2 /H2SO4 芳香伯胺 NH2 NaNO2/HCl(aq.) 0-5 C o N2 + Cl - + NaCl 氯化重氮苯 Diazonium Salt 重氮盐 重氮化反应 Diazotization HONO + H + HO NO H + NO + H2O Ar NH2 + NO Ar N NO H H -H + Ar N N H O Ar N N OH + H + Ar N N OH2 -H2O Ar N N Mechanism