4-苯基-3H-1,2,4-三唑啉-3,5-二酮

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

实验步骤: 投料: 将奥氮平（10mol）溶于乙酸乙酯（500ml)中，控温至20-25℃，随后加入PTAD（1.3mmo)混合形成土黄色浑浊，搅拌10min，向上述EA溶液中加入等量的0.1%TFA水溶液，将两相混合物在室温下搅拌15min。配比6%碳酸氢钠水溶液（1.2g/20ml) 送样需加入两滴碳酸氢钠水溶液淬灭加入EA萃取，有机相送样HPLC监测反应进程，（M-C4X-117811和M-C4X-117820大概含量分别为38%，8%），停止反应，TLC监测反应（DCM:MEOH=10：1）117811产物点与原料点有分离度，117820与原料点同出，将剩余碳酸氢钠水溶液加入体系淬灭反应，加入EA萃取，收集有机相干燥浓缩。 将粗品拌样硅胶粉经柱层析纯化(DCM:MEOH=70:1)冲出117811产物，收集浓缩，后续有117811产物和原料点交叉，分开收集，将117811全部冲出后将洗脱液梯度升至DCM:MEOH=10:1将剩余原来点冲出，收集浓缩。

实验步骤: 投料: 将奥氮平（1mol）溶于乙酸乙酯（50ml)中，控温至20-25℃，随后加入PTAD（1.3mmo)混合形成土黄色浑浊，搅拌10min，向上述EA溶液中加入等量的0.1%TFA水溶液，将两相混合物在室温下搅拌15min。配比6%碳酸氢钠水溶液（0.12g/2ml) 送样需加入两滴碳酸氢钠水溶液淬灭加入EA萃取，有机相送样HPLC监测反应进程，（M-C4X-117811和M-C4X-117820大概含量分别为38%，8%），停止反应，TLC监测反应（DCM:MEOH=10：1）117811产物点与原料点有分离度，117820与原料点同出，将剩余碳酸氢钠水溶液加入体系淬灭反应，加入EA萃取，收集有机相干燥浓缩。

实验步骤: 投料: 将奥氮平（5g，1.0eq）溶于乙酸乙酯（800ml)中，控温至20-25℃，随后加入PTAD（3.64g，1.3eq)混合形成土黄色浑浊，搅拌10min，向上述EA溶液中加入等量的0.1%TFA水溶液，将两相混合物在室温下搅拌15min。配比6%碳酸氢钠水溶液（1.92g/32ml) 送样需加入两滴碳酸氢钠水溶液淬灭加入EA萃取，有机相送样HPLC监测反应进程，（M-C4X-117811和M-C4X-117820大概含量分别为42%，6%），停止反应，TLC监测反应（DCM:MEOH=10：1）117811产物点与原料点有分离度，117820与原料点同出，将剩余碳酸氢钠水溶液加入体系淬灭反应，加入EA萃取，收集有机相干燥浓缩。 将粗品拌样硅胶粉经柱层析纯化(DCM:MEOH=70:1)冲出117811产物，收集浓缩，后续有117811产物和原料点交叉，分开收集，将117811全部冲出后将洗脱液梯度升至DCM:MEOH=10:1将剩余原料点冲出，收集浓缩。 117811过柱所得粗品送样HPLC和核磁发现明显杂质，加入纯乙酸乙酯（15ml）打浆三次，收集滤饼冻干。 2026/05/15 送检三谱+定量（M-C4X-117811)数据均达标，入库3.4g黄色固体。

实验步骤: 投料: 分别在5个两升桶：将奥氮平（5g，1.0eq）溶于乙酸乙酯（800ml)中，控温至20-25℃，随后加入PTAD（4.2g，1.5eq)混合形成土黄色浑浊，搅拌10min，向上述EA溶液中加入等量的0.1%TFA水溶液，将两相混合物在室温下搅拌15min。配比6%碳酸氢钠水溶液（1.92g/32ml) 送样需加入两滴碳酸氢钠水溶液淬灭加入EA萃取，有机相送样HPLC监测反应进程，（M-C4X-117820-1大概含量分别为34%），停止反应，将剩余碳酸氢钠水溶液加入体系淬灭反应，过滤体系，收集滤液，加入EA萃取，收集有机相干燥浓缩。

实验步骤: 投料: 分别在5个两升桶：将奥氮平（5g，1.0eq）溶于乙酸乙酯（800ml)中，控温至20-25℃，随后加入PTAD（4.2g，1.5eq)混合形成土黄色浑浊，搅拌10min，向上述EA溶液中加入等量的0.1%TFA水溶液，将两相混合物在室温下搅拌15min。配比6%碳酸氢钠水溶液（1.92g/32ml) 1个两升桶：将奥氮平（3.12g，10mol）溶于乙酸乙酯（500ml)中，控温至20-25℃，随后加入PTAD（1.5mmo)混合形成土黄色浑浊，搅拌10min，向上述EA溶液中加入等量的0.1%TFA水溶液，将两相混合物在室温下搅拌15min。配比6%碳酸氢钠水溶液（1.2g/20ml) 送样需加入两滴碳酸氢钠水溶液淬灭加入EA萃取，有机相送样HPLC监测反应进程，（M-C4X-117820-1大概含量分别为40%），停止反应，将剩余碳酸氢钠水溶液加入体系淬灭反应，过滤体系，收集滤液，加入EA萃取，收集有机相干燥浓缩。

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 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)