Azidotrimethylsilane → 4,4-dimethyl-6-fluoro-8-nitro-4H-benzo[b]tetrazolo[1,5-d][1,4]oxazine

HRID 1754411ノート

反応式

HRID 1754411 の反応式
[F:1][C:2]1[C:7]2[O:8][C:9]([CH3:14])([CH3:13])[C:10](=S)[NH:11][C:6]=2[CH:5]=[C:4]([N+:15]([O-:17])=[O:16])[CH:3]=1.[Si]([N:22]=[N+:23]=[N-:24])(C)(C)C>C1COCC1.[Hg](OC(C)=O)OC(C)=O.CCOC(C)=O>[CH3:13][C:9]1([CH3:14])[O:8][C:7]2[C:2]([F:1])=[CH:3][C:4]([N+:15]([O-:17])=[O:16])=[CH:5][C:6]=2[N:11]2[N:22]=[N:23][N:24]=[C:10]12

参加物

6

反応物 2

HCID 78378AzidotrimethylsilaneHCID 898638698-Fluoro-2,2-dimethyl-6-nitro-2H-benzo[b][1,4]oxazin-3(4H)-thione

生成物 1

HCID 904376754,4-dimethyl-6-fluoro-8-nitro-4H-benzo[b]tetrazolo[1,5-d][1,4]oxazine収率 57%

試薬・触媒・溶媒 3

HCID 8028Tetrahydrofuran溶媒HCID 8857Ethyl Acetate溶媒HCID 16683746Diacetyloxymercury溶媒

実験手順

To a solution of 8-fluoro-2,2-dimethyl-6-nitro-2H-benzo[b][1,4]oxazin-3(4H)-thione (1.0 g, 3.9 mmol) in THF, Hg(OAc)2 was added at 0° C. TMS-N3 was added to the reaction mixture at 0° C. and stirred for 1 hour. Reaction mixture was allowed to warm to room temperature and stirred for 3 hours. LCMS analysis of the reaction mixture indicated completion of the reaction. After 3 hours, the reaction mixture was diluted with 100 ml of EtOAc and partitioned with saturated aqueous NH4Cl (100 ml). Layers were separated and the aqueous layer was washed twice with EtOAc (50 ml). Combined EtOAc layers were dried over Na2SO4 and concentrated. The crude product was purified by column chromatography to give the product in 57% yield (0.57 g). LCMS (m/z) 266 (MH+).

後処理

  1. customReaction mixture
  2. stirringstirred for 3 hours
  3. customcompletion of the reaction
  4. waitAfter 3 hours
  5. custompartitioned with saturated aqueous NH4Cl (100 ml)
  6. customLayers were separated
  7. washthe aqueous layer was washed twice with EtOAc (50 ml)
  8. dry with materialCombined EtOAc layers were dried over Na2SO4
  9. concentrationconcentrated
  10. customThe crude product was purified by column chromatography
  11. customto give the product in 57% yield (0.57 g)

出典と根拠

ORDレコード
ord-64653c725c894a67bae572ca25eba64f
出典データセット
uspto-grants-2015_10
特許番号
US09169249B2

反応ノート

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