Citric Acid → 3-[3-(5-Chloro-2-methoxyphenylsulfonyloxy)-5-methylphenoxy]propionaldehyde

HRID 442940ノート

反応式

HRID 442940 の反応式
[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([O:24][CH3:25])=[C:6]([S:8]([O:11][C:12]2[CH:13]=[C:14]([CH:20]=[C:21]([CH3:23])[CH:22]=2)[O:15][CH2:16][CH2:17][CH2:18][OH:19])(=[O:10])=[O:9])[CH:7]=1.C(N(CC)C(C)C)(C)C.CS(C)=O.C(O)(=O)CC(CC(O)=O)(C(O)=O)O>ClCCl>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([O:24][CH3:25])=[C:6]([S:8]([O:11][C:12]2[CH:13]=[C:14]([CH:20]=[C:21]([CH3:23])[CH:22]=2)[O:15][CH2:16][CH2:17][CH:18]=[O:19])(=[O:9])=[O:10])[CH:7]=1

参加物

6

反応物 4

HCID 311Citric AcidHCID 679Dimethyl SulfoxideHCID 81531DiisopropylethylamineHCID 227224523-[3-(5-Chloro-2-methoxyphenylsulfonyloxy)-5-methylphenoxy]propanol

生成物 1

HCID 539733043-[3-(5-Chloro-2-methoxyphenylsulfonyloxy)-5-methylphenoxy]propionaldehyde収率 71%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

反応条件

温度
0 °C

実験手順

To a cooled (0° C.) solution of 3-[3-(5-chloro-2-methoxyphenylsulfonyloxy)-5-methylphenoxy]propanol (3.32 g, 8.58 mmol), N,N-diisopropylethylamine (3.14 mL, 18.0 mmol), and anhydrous dimethyl sulfoxide (1.83 mL, 25.7 mmol) in anhydrous dichloromethane (20 mL) under nitrogen was added sulfur trioxide pyridine complex (2.73 g, 17.1 mmol) portionwise over 23 minutes. The solution was stirred at 0° C. for 1 hour then quenched with 5% w/v aqueous citric acid (200 mL, 48 mmol). The mixture was extracted with diethyl ether (250 mL). The aqueous layer was extracted with diethyl ether (2×100 mL), and the combined organic extracts were washed with pH 7 buffer (100 mL) and brine (100 mL). The organic layer was dried over Na2SO4, filtered, and evaporated. Crude product was purified by flash column chromatography through silica gel (50% to 70% diethyl ether in hexane) to give the title compound as a gold oil (2.34 g, 71%). 1H-NMR (300 MHz, CDCl3) δ 9.81 (t, 1 H, J=1.5 Hz), 7.79 (d, 1 H, J=2.7 Hz), 7.54 (dd, 1 H, J=2.7, 8.9 Hz), 7.01 (d, 1 H, J=8.9 Hz), 6.54-6.60 (m, 1 H), 6.52-6.53 (m, 1 H), 6.43-6.44 (m, 1 H), 4.19 (t, 2 H, J=6.1 Hz), 3.99 (s, 3 H), 2.85 (td, 2 H, J=1.5, 6.1 Hz), 2.25 (d, 3 H, J=0.5 Hz). Mass spectrum (MALDI-TOF, α-cyano4- hydroxycinnamic acid matrix) calcd. for C17H17ClO6S: 407.0 (M+Na). Found: 407.0.

後処理

  1. additionwas added sulfur trioxide pyridine complex (2.73 g, 17.1 mmol) portionwise over 23 minutes
  2. extractionThe mixture was extracted with diethyl ether (250 mL)
  3. extractionThe aqueous layer was extracted with diethyl ether (2×100 mL)
  4. washthe combined organic extracts were washed with pH 7 buffer (100 mL) and brine (100 mL)
  5. dry with materialThe organic layer was dried over Na2SO4
  6. filtrationfiltered
  7. customevaporated
  8. customCrude product was purified by flash column chromatography through silica gel (50% to 70% diethyl ether in hexane)

出典と根拠

ORDレコード
ord-6b84561ef91b437c8a50364938af4d20
出典データセット
uspto-grants-1999_04
特許番号
US05891909

反応ノート

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