Nitric Acid → HCID 89419880、化合物

反応式

[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C@@:8]1([CH3:20])[N:16]=[C:15]([NH2:17])[C:11]2([CH2:14][CH2:13][CH2:12]2)[S:10](=[O:19])(=[O:18])[CH2:9]1.S(=O)(=O)(O)O.[N+:26]([O-])([OH:28])=[O:27].[OH-].[Na+]>>[F:1][C:2]1[CH:7]=[CH:6][C:5]([N+:26]([O-:28])=[O:27])=[CH:4][C:3]=1[C@@:8]1([CH3:20])[N:16]=[C:15]([NH2:17])[C:11]2([CH2:12][CH2:13][CH2:14]2)[S:10](=[O:19])(=[O:18])[CH2:9]1

参加物

反応物 4

HCID 944Nitric Acid

HCID 1118Sulfuric Acid

HCID 14798Sodium Hydroxide

HCID 90024450HCID 90024450、化合物

生成物 1

HCID 89419880HCID 89419880、化合物収率 106.2%

反応条件

温度: 0 °C

実験手順

(R)-7-(2-Fluoro-phenyl)-7-methyl-5,5-dioxo-5λ6-thia-8-aza-spiro[3.5]non-8-en-9-ylamine (385 mg, 1.3 mmol, Eq: 1.00) was dissolved in conc. sulfuric acid (6.37 g, 3.46 ml, 65.0 mmol, Eq: 50). At 0° C., fuming nitric acid (123 mg, 87.1 μl, 1.95 mmol, Eq: 1.5) was added dropwise. The light brown solution was stirred at 0° C. for 2 hours. The reaction mixture was poured on ice and basified with 3 N NaOH followed by extraction with dichloromethane. The organic layer was separated, dried over Na2SO4, filtered and evaporated to dryness to give the crude and pure (R)-7-(2-fluoro-5-nitro-phenyl)-7-methyl-5,5-dioxo-5λ6-thia-8-aza-spiro[3.5]non-8-en-9-ylamine (470 mg, 1.38 mmol, 106% yield) as a light brown foam. MS (ISP): m/z=342.1 [M+H]+.