Sulfuryl chloride → tert-butyl N-[3-(chlorosulfonyl)phenyl]-N-methylcarbamate

HRID 29190

反応式

HRID 29190 の反応式
Br[C:2]1[CH:3]=[C:4]([CH:14]=[CH:15][CH:16]=1)[N:5]([C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8])[CH3:6].C([Li])CCC.[S:22](Cl)([Cl:25])(=[O:24])=[O:23]>C1COCC1>[C:10]([O:9][C:7]([N:5]([CH3:6])[C:4]1[CH:14]=[CH:15][CH:16]=[C:2]([S:22]([Cl:25])(=[O:24])=[O:23])[CH:3]=1)=[O:8])([CH3:13])([CH3:12])[CH3:11]

参加物

5

反応物 3

HCID 24648Sulfuryl chlorideHCID 22997148N-BOC-N-Methyl-3-bromoanilineHCID 178418339Butyllithium

生成物 1

HCID 22996452tert-butyl N-[3-(chlorosulfonyl)phenyl]-N-methylcarbamate

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
-78 °C

実験手順

3-Bromo-N-tert-butoxycarbonyl-N-methylaniline (0.358 g, 1.2 mmol) was dissolved in freshly distilled THF (5 ml) under a N2 atmosphere. The solution was chilled to −78° C. and n-butyl lithium (0.750 ml, 2.0 M solution in cyclohexane, 1.5 mmol) was added. After 15 minutes, sulfuryl chloride (0.121 ml, 1.5 mmol) was added and the reaction was allowed to warm to room temperature and stirring was continued overnight. THF was removed by evaporation and the resulting residue was diluted in EtOAc. Organic phase was washed with H2O and brine before being dried with MgSO4. The solvent was removed in vacuo. Purification by flash chromatography (1:19/EtOAc/Hex gradient to 1:9 and then to 1:4). Recovered 0.089 g (23%) of the product as a colorless oil. Rf=0.14 (1:9 EtOAc/Hex). 1H NMR (CDCl3) 7.96 (1H,s), 7.80 (1H,d), 7.68 (1H,d), 7.57 (1H,t), 3.33 (3H,s), 1.50 (9H,s).

後処理

  1. temperatureto warm to room temperature
  2. waitwas continued overnight
  3. customTHF was removed by evaporation
  4. additionthe resulting residue was diluted in EtOAc
  5. washOrganic phase was washed with H2O and brine
  6. dry with materialbefore being dried with MgSO4
  7. customThe solvent was removed in vacuo
  8. customPurification by flash chromatography (1:19/EtOAc/Hex gradient to 1:9
  9. customRecovered 0.089 g (23%) of the product as a colorless oil

出典と根拠

ORDレコード
ord-950b4dc6d8054b6cb3d25456521aec7b
出典データセット
uspto-grants-2008_09
特許番号
US07419967B2

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