厦门大学化学化工学院：《有机化学》课程教学资源（课件讲稿，双语版）第十三章 含氮芳香化合物 Aromatic Nitrogen Compounds（3/3）

133芳香重氮盐在合成上的应用

Organic Chemistry Organic Chemistry Xiamen Xiamen University University 13.3 芳香重氮盐在合成上的应用

Br N≡NHSO4 芳香重氮盐 Arenediazonium salt ①D ⑨D H OH CN

Organic Chemistry Organic Chemistry Xiamen Xiamen University University N N HS O 4 + OH 芳香重氮盐 Arenediazon ium s alt CN Cl Br I H

Hydrolysis HO N≡NHSO4 -OH +N2 Mechanism HoO N≡N一→ OH ①D ⑨D OH

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Hydrolysis Hydrolysis N N HSO 4 + H 2 O OH H + + N 2 Mechanism Mechanism N N + + H 2 O OH 2 + -H + OH

Sandmeyer Reaction CuCl N≡NCl Cl+ n HCL A CuBr N三NBr Br t N HBr.△ 2 KI N≡NHSO I n2

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Sandmeyer Sandmeyer Reaction Reaction N N Cl + Cl CuC l HCl, ∆ + N 2 N N Br + Br CuBr HB r, ∆ + N 2 N N HS O 4 + KI I + N 2

Gatterman Reaction CuCN N三NCl K CN CN N2 Schiemann Reaction HBE N≡NCl N三NBF 4 ①D ⑨D F+ N2

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Gatterman Gatterman Reaction eaction N N Cl + CuCN KC N CN + N 2 Schiemann Schiemann Reaction eaction N N Cl + HB F 4 N N BF 4 + ∆ F + N 2

Olah Reaction CH CH3 35~37 N≡NBC4 Cl n, +bCI 77.6% CH CH 128~134 N≡NBBr4 ①D 一Br+N2+BBr3 ⑨D 96.5

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Olah Reaction Olah Reaction N N BCl4 - + CH 3 35~37 Cl CH 3 N N BBr4 - + CH 3 128~134 Br CH 3 + N 2 + BCl 3 + N 2 + BBr 3 77.6% 96.5%

Meerwein Reaction Cuc N≡NCI+ -CH-CHCN 10~30 CI CN HCI CHCH-〈 CH-C

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Meerwein Reaction Meerwein Reaction N N Cl - + + CH CHCN CuCl 2 10 ~ 3 0 CH CH Cl CN CH C CN -HCl

○ Replacement by Hydrogen 03 Deamination by diazotization 三. Arenediazonium salts react with hypophosphorous acid (H3P02) to yield products in which the diazonium group has been replaced by-—H EtOH /Zn N≡NCl H or HPO 2

Organic Chemistry Organic Chemistry Xiamen Xiamen University University Replacement by Hydrogen —— Deamination by diazotization Replacement by Hydrogen —— Deamination by diazotization „ Arenediazonium salts react with hypophosphorous acid (H3PO2) to yield products in which the diazonium group has been replaced by — H N N Cl - + EtOH / Z n or H 3PO 2 H

HNO3 [H Ac20 Cl2 CH H3o hno2 CH3 NHCocH H2PO 2 CH2-

Organic Chemistry Organic Chemistry Xiamen Xiamen University University H 3PO 2 CH 3 HNO 3 [H ] Ac 2 O Cl 2 CH 3 NHCOCH 3 Cl H 3 O + HNO 2 CH 3 Cl

NH2 NH 2 3Br Br BI NanO,/H2 sO4 0~5 Br NHSO Br Br H3PO, Br Br Br Br

Organic Chemistry Organic Chemistry Xiamen Xiamen University University NH 2 3Br 2 NH 2 Br Br Br NaNO 2/H 2SO 4 0 ~ 5 N 2HSO 4 - Br Br Br H 3PO 2 Br Br Br