4-phenyl-1,2,4-triazole-3,5-dione

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 140.3 g of the 1α,2α-epoxide of the 1,4-cyclic adduct of cholesta-1,5,7-triene-3β,25-diol and 4-phenyl-1,2,4-triazoline-3,5-dione obtained in Example 2 was dissolved in 15 ml of tetrahydrofuran, and 142 mg of lithium aluminum hydride was added little by little to the solution under agitation. Then, the mixture was mildly refluxed and boiled for 1 hour and cooled, and 20 ml of tetrahydrofuran was added to the reaction mixture. A saturated aqueous solution of Glauber salt was added to the reaction mixture until generation of bubbles was stopped, whereby excessive lithium aluminum hydride was decomposed. The reaction mixture was then filtered, and the residue was washed 3 times with 10 ml of tetrahydrofuran. The organic solvent layer was dried and the solvent was distilled off. The residue was purified by using a column packed with 20 g of Sephadex LH 20, and a fraction eluted by chloroform-hexane (65 : 35 V/V ratio) was collected and recrystallized from ether-hexane to obtain 49.9 mg of cholesta-5,7-diene-1α,3β,25-triol in the form of needles melting at 149° to 152° C. Then, the mixture was mildly refluxed cooled A saturated aqueous solution of Glauber salt was added to the reaction mixture until generation of bubbles The reaction mixture was then filtered the residue was washed 3 times with 10 ml of tetrahydrofuran The organic solvent layer was dried the solvent was distilled off The residue was purified a fraction eluted by chloroform-hexane (65 : 35 V/V ratio) was collected recrystallized from ether-hexane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To 1α,3β-bis(tert-butyldimethylsilyloxy)-17β-{4-ethyl-4-(triethylsilyloxy)hexyloxymethyl}androst-5-ene (1.0 g), were added hexane (15 ml), N-bromosuccinimide (336.4 mg) and then 2,2′-azobis isobutyronitrile (77.6 mg), followed by reaction under reflux for 30 min. After cooling with ice, the mixture was filtered to remove insoluble material and the filtrate was evaporated under reduced pressure to remove the solvent. To the resulting residue, were added toluene (10 ml) and γ-collidine (534.4 mg), followed by reflux for 2 hours. The mixture was filtered to remove insoluble material and the filtrate was diluted with hexane. The organic layer was washed with IM hydrochloric acid, a saturated aqueous sodium bicarbonate solution and then saturated brine and evaporated to remove the solvent under reduced pressure. The resulting residue was purified by column chromatography (hexane:ethyl acetate 40:1), dissolved in dichloromethane (20 ml) and subjected to reaction for 1 hour by adding 4-phenyl-1,2,4-triazoline-3,5-dione. The reaction mixture was evaporated to remove the solvent under reduced pressure and the resulting residue was purified by column chromatography (hexane:ethyl acetate=7:1) to give the titled compound (0.45 g). under reflux for 30 min After cooling with ice the mixture was filtered to remove insoluble material the filtrate was evaporated under reduced pressure to remove the solvent To the resulting residue, were added toluene (10 ml) and γ-collidine (534.4 mg) by reflux for 2 hours The mixture was filtered to remove insoluble material the filtrate was diluted with hexane The organic layer was washed with IM hydrochloric acid a saturated aqueous sodium bicarbonate solution and then saturated brine and evaporated to remove the solvent under reduced pressure The resulting residue was purified by column chromatography (hexane:ethyl acetate 40:1) dissolved in dichloromethane (20 ml) subjected to reaction for 1 hour The reaction mixture was evaporated to remove the solvent under reduced pressure the resulting residue was purified by column chromatography (hexane:ethyl acetate=7:1)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Phenylurazole (25gm) and anhydrous sodium sulphate were suspended in methylene chloride. The suspension was cooled in ice and nitrogen dioxide was passed in until all the 4-phenylurazole dissolved. The solution was filtered and the solvent removed under reduced pressure. The solid was either used as obtained or purified by sublimation (at 100°C and 10-5 mm of mercury). The suspension was cooled in ice dissolved The solution was filtered the solvent removed under reduced pressure as obtained purified by sublimation (at 100°C and 10-5 mm of mercury)

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a solution of phenol (11.3 mg, 0.120 mmol) in 100 mM pH 7.0 NaH2PO4/Na2HPO4 buffer (3.0 mL)-CH3CN (3.0 mL) was slowly dropped the 0.3 M solution of PTAD 17a (0.442 mL, 0.132 mmol) in CH3CN at room temperature. The resulting solution was stirred at room temperature for 30 minutes. The reaction mixture was acidified with 1M HCl and extracted with ethyl acetate twice. The organic layer was dried over Na2SO4 and concentrated in vacuo. The obtained crude material was purified by flash column chromatography (ethyl acetate) to give para-adduct 27 (4.8 mg, 15%) and para-ortho-di-adduct 27′ (10.1 mg, 19%) as a white solid. 1H NMR (300 MHz, DMSO-d6): δ 11.35 (br, 1H), 9.60 (s, 1H), 7.53-7.35 (m, 7H), 6.83 (m, 2H), 13C NMR (75 MHz, DMSO-d6): δ 156.11, 152.73, 150.41, 132.22, 129.22, 128.78, 128.66, 127.19, 122.99, 116.22. HRMS: calcd for C14H11N3O3 (MH+) 270.0873. found 270.0873. extracted with ethyl acetate twice The organic layer was dried over Na2SO4 concentrated in vacuo The obtained crude material was purified by flash column chromatography (ethyl acetate)