hydrogen azide; chloroform; sulfuric acid

2,2,6,6-tetramethyl-1-piperidinyloxy, free radical; calcium methanolate in acetonitrile T=0 - 20°C;

acetic acid T=30°C; E(activ.), ΔH(activ.), ΔS(activ.), Γ(activ.); KineticsMechanismThermodynamic data;

acetic acid T=30°C; E(activ.), ΔH(activ.), ΔS(activ.), Γ(activ.); KineticsMechanismThermodynamic data;

Tris-HCl buffer; NADH-H+; 1,4-dithio-DL-threitol; female Sprague-Dawley rat mammary gland cytosol in dimethyl sulfoxide T=37°C; pH=7.4; Enzyme kinetics;

aluminum isopropoxide in isopropyl alcohol Reduction; 2 h; Heating;

1: 2.) 2 M aq. Na2CO3 / 1.) Pd(PPh3)4 / 1.) EtOH, DME, 10 min, 2.) reflux, 20 h 2: 73 percent / NBS / benzoyl peroxide / CCl4 / 36 h / Heating 3: AgNO3 / dioxane; H2O / 18 h / Ambient temperature 4: aq. KOH / dioxane / 20 h / Ambient temperature 5: 72 percent / aq. KMnO4 / acetone / 4 h / Ambient temperature 6: 66 percent / polyphosphoric acid / 5 h / 160 °C 7: 64.5 percent / Et3SiH / trifluoroacetic acid / 48 h / Ambient temperature View Scheme

1: 2.) 2 M aq. Na2CO3 / 1.) Pd(PPh3)4 / 1.) EtOH, DME, 10 min, 2.) reflux, 20 h 2: 73 percent / NBS / benzoyl peroxide / CCl4 / 36 h / Heating 3: AgNO3 / dioxane; H2O / 18 h / Ambient temperature 4: aq. KOH / dioxane / 20 h / Ambient temperature 5: 72 percent / aq. KMnO4 / acetone / 4 h / Ambient temperature 6: 66 percent / polyphosphoric acid / 5 h / 160 °C 7: 64.5 percent / Et3SiH / trifluoroacetic acid / 48 h / Ambient temperature View Scheme

1: 73 percent / NBS / benzoyl peroxide / CCl4 / 36 h / Heating 2: AgNO3 / dioxane; H2O / 18 h / Ambient temperature 3: aq. KOH / dioxane / 20 h / Ambient temperature 4: 72 percent / aq. KMnO4 / acetone / 4 h / Ambient temperature 5: 66 percent / polyphosphoric acid / 5 h / 160 °C 6: 64.5 percent / Et3SiH / trifluoroacetic acid / 48 h / Ambient temperature View Scheme

1: 2.) 2 M aq. Na2CO3 / 1.) Pd(PPh3)4 / 1.) EtOH, DME, 10 min, 2.) reflux, 20 h 2: 72 percent / aq. KMnO4 / acetone / 4 h / Ambient temperature 3: 66 percent / polyphosphoric acid / 5 h / 160 °C 4: 64.5 percent / Et3SiH / trifluoroacetic acid / 48 h / Ambient temperature View Scheme