Chloroacetyl chloride → HCID 10980869、化合物

HRID 1108165ノート

反応式

HRID 1108165 の反応式
[F:1][CH:2]([F:18])[S:3]([C:6]1[CH:11]=[CH:10][C:9]([C:12]2[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=2)=[CH:8][CH:7]=1)(=[O:5])=[O:4].[Cl:19][CH2:20][C:21](Cl)=[O:22].[Cl-].[Al+3].[Cl-].[Cl-]>ClCCl>[Cl:19][CH2:20][C:21]([C:15]1[CH:16]=[CH:17][C:12]([C:9]2[CH:8]=[CH:7][C:6]([S:3]([CH:2]([F:1])[F:18])(=[O:5])=[O:4])=[CH:11][CH:10]=2)=[CH:13][CH:14]=1)=[O:22]

参加物

5

反応物 3

HCID 6577Chloroacetyl chlorideHCID 6451240Aluminum(III) ChlorideHCID 10858478HCID 10858478、化合物

生成物 1

HCID 10980869HCID 10980869、化合物収率 82%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

反応条件

温度
27.5 °C

実験手順

To a 500-mL sidearm flask equipped with a vented addition funnel, overhead stirrer, thermometer, and nitrogen bubbler connected to a caustic scrubber was charged 26.8 g (0.098 mol, assay=98%) 4-[(difluoromethyl)sulfonyl]-1,1'-biphenyl, of 13.4 g (0.20 mol) of chloroacetyl chloride, and 150 mL of dichloromethane. Granular anhydrous aluminum chloride (28.0 g, 0.210 mol) was added in portions over 20 minutes, and the mixture was allowed to stir at 25-30° C. for 8-18 h. The violet solution was poured onto 300 g of ice with efficient stirring, 300 mL of dichloromethane was added to the resulting yellow slurry, and the mixture was filtered to remove undissolved 4'-(chloroacetyl)[1,1'-biphenyl]-4-sulfinic acid. After phase separation, the dichloromethane solution was washed with aqueous HCl, aqueous NaHCO3, dried with MgSO4, filtered, and concentrated to dryness. The residue was slurried in 200 mL of isopropanol, filtered, and washed with 50 mL of isopropanol to afford 27.7 g (ca. 79%) of crude 2-chloro-1-[4'-[(difluoromethyl)sulfonyl][1,1'-biphenyl]-4-yl]ethanone as a pale yellow solid assaying at 96% by gc-area. A 98%-pure sample was obtained by chromatography on silica-gel and crystallization from EtOAc/hexane, m.p. 157-159° C. IR(KBr) 1696, 1604, 1594, 1397, 1344, 1308, 1210, 1168, 1118, 1081, 999, 816, 750, 631 cm-1. UV (CH2Cl2): λmax =287 nm (ε=33.1×103) 1H-NMR (CDCl3): δ4.75 (s, 2H), 6.25 (t, 1H, J=60 Hz), 7.77 (d, 2H), 7.89 (d, 2H), 8.10 (2 d, 4H). 13C-NMR (DMSO-d6): δ47.6, 114.7 (t, JCF =283 Hz), 191.3 ppm. 19F-NMR (CDCl3): δ-121.6 ppm (d, JHF =53 Hz). Mass spectrum m/z=344 (M+), 295 (M+ --CH2Cl, base peak), 245, 229, 180, 165, 152 amu.

後処理

  1. customTo a 500-mL sidearm flask equipped with a vented addition funnel, overhead stirrer
  2. additionwas added to the resulting yellow slurry
  3. filtrationthe mixture was filtered
  4. customto remove undissolved 4'-(chloroacetyl)[1,1'-biphenyl]-4-sulfinic acid
  5. customAfter phase separation
  6. washthe dichloromethane solution was washed with aqueous HCl, aqueous NaHCO3
  7. dry with materialdried with MgSO4
  8. filtrationfiltered
  9. concentrationconcentrated to dryness
  10. filtrationfiltered
  11. washwashed with 50 mL of isopropanol

出典と根拠

ORDレコード
ord-133cf4eb506146978b34a60d3b9da5e0
出典データセット
uspto-grants-2000_05
特許番号
US06063932

反応ノート

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