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 Arenediazonium salts react with hypophosphorous acid (H3P02) to yield products in which the diazonium group has been replaced by-—H EtOH /Zn N≡NCl H or HPO 2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Arenediazonium salts react with hypophosphorous acid (H3PO2) to yield products in which the diazonium group has been replaced by — H N N Cl - + EtOH / Z n or H 3PO 2 H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
