上泽通大学 SHANGHAI JIAO TONG UNIVERSITY 4)Journal of Organic Chemistry (1986),51(15),2880-3. MeC6H4R(R=H,4-NO2,3-NO2,2-NO2,4-CI,2-CI,4-Br,2-Br,4-cyano),ring- substituted with electron-withdrawing substituents,were oxidized to RC6H4CO2H. The oxidn.system is biphasic consisting of an org.phase(CICH2CH2CI)and an aq. sodium hypochlorite phase with both Ru and quaternary ammonium salts acting as catalysts.Yields are essentially quant.after 2 h at room temp.with a hypochlorite to toluene ratio of 4.5:1 provided the pH of the aq.phase is maintained between 8.0 and 10.5.Kinetic studies show the reaction to be first order in the substrate,zero order in sodium hypochlorite,and combined first order in the catalysts.The reaction mechanism is also discussed. Me 1.1 R:Naocl,R:Bu4N+.Br-,R:H2S04,C:RuC13, CO2H S:C1CH2CH2C1,S:H20 1.2 R:NaO,S:H20 O2N NOTE:hydroxide maintains pH, Reactants:1,Reagents:4,Catalysts:1,Solvents:2, Steps:1,Stages:2
4) Journal of Organic Chemistry (1986), 51(15), 2880-3. MeC6H4R (R = H, 4-NO2, 3-NO2, 2-NO2, 4-Cl, 2-Cl, 4-Br, 2-Br, 4-cyano), ringsubstituted with electron-withdrawing substituents, were oxidized to RC6H4CO2H. Th id i bi h i i i f h (ClCH2CH2Cl) d The oxidn. system is biphasic consisting of an org. phase (ClCH2CH2Cl) and an aq. sodium hypochlorite phase with both Ru and quaternary ammonium salts acting as catalysts. Yields are essentially quant. after 2 h at room temp. with a hypochlorite to toluene ratio of 4.5:1 provided the pH of the aq. phase is maintained between 8.0 and toluene ratio of 4.5:1 provided the pH of the aq. phase is maintained between 8.0 and 10.5. Kinetic studies show the reaction to be first order in the substrate, zero order in sodium hypochlorite, and combined first order in the catalysts. The reaction mechanism is also discussed. Me 1.1 R:NaOCl, R:Bu4N+ Br-, R:H2SO4, C:RuCl3, CO2H • O2N 1.2 R:NaOH, S:H2O S:ClCH2CH2Cl, S:H2O O2N NOTE: hydroxide maintains pH, Reactants: 1, Reagents: 4, Catalysts: 1, Solvents: 2, Steps: 1, Stages: 2
上泽充通大学 SHANGHAI JIAO TONG UNIVERSITY 5)Zhurnal Prikladnoi Khimii(Sankt-Peterburg,Russian Federation)(1988), 61(5),1069-73. ·6)U.S.S.R.(1988), Oxidn.of RMe(R=p-O2NC6H4,2,4-CI2C6H3)to RCO2H(same R)with 35%HNO3 at 200 proceeded with an induction period followed by rapid reaction and attenuation.The induction period was reduced to a diffusion- controlled min.by mixing preheated reactants.Rapid cooling of the reaction mixt.to 20 decreased byproduct formation.Math.and graphical representations of the process were given. Me CO2H R:HNO3,S:H20 O2N O2N NOTE:Reactants:1,Reagents:1,Solvents:1, steps:1,stages:1
• 5) Zhurnal Prikladnoi Khimii (Sankt-Peterburg, Russian Federation) (1988), 61(5), 1069-73. • 6) ( ), U.S.S.R. (1988), • Oxidn. of RMe (R = p-O2NC6H4, 2,4-Cl2C6H3) to RCO2H (same R) with 35% HNO3 at 200 ° proceeded with an induction period followed by rapid reaction and attenuation. The induction period was reduced to a diffusion reaction and attenuation. The induction period was reduced to a diffusion - controlled min. by mixing preheated reactants. Rapid cooling of the reaction mixt. to 20 ° decreased byproduct formation. Math. and graphical re p pg resentations of the process were given. M e C O 2 H O 2 N R:H N O 3, S:H 2 O O 2 N N O T E: R e a c t a n t s: 1, R e a g e n t s: 1, S o l v e n t s: 1, S t e p s: 1, S t a g e s: 1