Sodium hydride → 4-(4-Nitro-phenyl)-1,1-dioxo-hexahydro-1lambda6-thiopyran-4-carbonitrile

HRID 536969

反応式

HRID 536969 の反応式
[H-].[Na+].[N+:3]([C:6]1[CH:11]=[CH:10][C:9]([CH2:12][C:13]#[N:14])=[CH:8][CH:7]=1)([O-:5])=[O:4].Br[CH2:16][CH2:17][S:18]([CH2:21][CH2:22]Br)(=[O:20])=[O:19]>CS(C)=O.C1COCC1>[N+:3]([C:6]1[CH:7]=[CH:8][C:9]([C:12]2([C:13]#[N:14])[CH2:22][CH2:21][S:18](=[O:20])(=[O:19])[CH2:17][CH2:16]2)=[CH:10][CH:11]=1)([O-:5])=[O:4]

参加物

6

反応物 3

HCID 24758Sodium hydrideHCID 68386p-NitrophenylacetonitrileHCID 1390521-Bromo-2-(2-bromoethanesulfonyl)ethane

生成物 1

HCID 589949324-(4-Nitro-phenyl)-1,1-dioxo-hexahydro-1lambda6-thiopyran-4-carbonitrile収率 98.3%

試薬・触媒・溶媒 2

HCID 679Dimethyl Sulfoxide溶媒HCID 8028Tetrahydrofuran溶媒2 回

実験手順

A slurry of NaH (71.4 mg, 1.79 mmol, 60% dispersion) in DMSO (3 mL) and THF (1 mL) was treated with solid (4-nitro-phenyl)-acetonitrile (121 mg, 0.744 mmol) and stirred at RT for 3 min. A solution of 1-bromo-2-(2-bromoethanesulfonyl)-ethane (250 mg, 0.893 mmol) in THF (3 mL) was added, and the mixture was heated to 70° C. for 1.5 h. The mixture was partitioned between EtOAc (100 mL) and water (75 mL), and brine (25 mL) was added. The aqueous layer was extracted with EtOAc (1×50 mL). The combined organic layers were dried over MgSO4 and concentrated in vacuo. Silica gel chromatography of the residue on a 20-g Isolute SPE column with 10-50% EtOAc-hexane afforded the title compound (205 mg, 98%) as a white solid. 1H-NMR (CDCl3; 400 MHz): δ 8.33 (d, 2H, J=8.8 Hz), 7.75 (d, 2H, J=8.8 Hz), 3.64-3.52 (m, 2H), 3.29-3.19 (m, 2H), 2.88-2.76 (m, 2H), 2.54-2.44 (m, 2H).

後処理

  1. temperaturethe mixture was heated to 70° C. for 1.5 h
  2. customThe mixture was partitioned between EtOAc (100 mL) and water (75 mL), and brine (25 mL)
  3. additionwas added
  4. extractionThe aqueous layer was extracted with EtOAc (1×50 mL)
  5. dry with materialThe combined organic layers were dried over MgSO4
  6. concentrationconcentrated in vacuo

出典と根拠

ORDレコード
ord-e4f0fccac76b4ab58a7b51bfd973badd
出典データセット
uspto-grants-2014_10
特許番号
US08859602B2

関連ノート

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