H20NH3ZIH2SH20H2SNH3
O S N H H2 O NH3 H2 S NH3 H2 S H2 O
TsOH甲苯，△t-BuBu-tt-BuBu-OH-H20t-BuBu-t80%MeMe1700CP2S5MeMeMeM40%NH3甲苯MeMeNMeMH90%
80% t-Bu O O Bu-t TsOH 甲 苯 , t-Bu OHO Bu-t . t-Bu O Bu-t OH -H2O t-Bu O Bu-t Me O O Me Me + P2 S5 170oC Me S Me Me Me O O Me + NH3 甲 苯 Me N Me H 40% 90%
15.2.1.5 Application in Organic Synthesis(1) Synthesis of Alkane andCycloalkaneRaneyNiR-CHCH,CH,CH-R + NiSRSR
15.2.1.5 Application in Organic Synthesis (1) Synthesis of Alkane and Cycloalkane Raney Ni R S R 1 2 4 3 5 R CH2 CH2 CH2 CH2 R + NiS 5 4 3 2
Zn-Hg酰基化开环COOHHCIAmdt-Eistert反应COOHCHgMgl(CH2)15CH31.-H20(CH2)15CHa(CH2)15CH2.RaneyNi
O 酰基化 O O 开 环 O COOH COOH C Cl O S (CH2 )15CH3 O CH3MgI S (CH2 )15CH3 H3C OH 1. -H2O 2. Raney Ni (CH2 )15CH3 Zn-Hg HCl Arndt-Eistert反 应 S (CH2 )15CH3
0=O=NaRaney Ni(CH2)4(CH2)4(CH2)4MeOC(CH2)4(CH2)4COMe(CH2)4HOO
MeOC(CH2 )4 S O (CH2 )4COMe O Na S (CH2 )4 (CH2 )4 HO O Raney Ni (CH2 )4 (CH2 )4