Dimethyl Sulfoxide → 3-Methoxyphthalaldehyde

HRID 505251ノート

反応式

HRID 505251 の反応式
CS(C)=O.C(Cl)(=O)C(Cl)=O.[OH:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([O:19][CH3:20])[C:14]=1[CH2:21][OH:22].C(N(CC)CC)C>C(Cl)Cl.O>[CH3:20][O:19][C:15]1[CH:16]=[CH:17][CH:18]=[C:13]([CH:12]=[O:11])[C:14]=1[CH:21]=[O:22]

参加物

7

反応物 4

HCID 679Dimethyl SulfoxideHCID 8471TriethylamineHCID 65578Oxalyl chlorideHCID 14892485(3-Methoxy-1,2-phenylene)dimethanol

生成物 1

HCID 203918283-Methoxyphthalaldehyde収率 95.1%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6344Dichloromethane溶媒3 回

実験手順

A solution of DMSO (63.35 g, 810.8 mmol, 4.4 equiv) in CH2Cl2 (190 ml) was slowly added at −78° C. under an atmosphere of argon to a solution of oxalyl chloride (51.46 g, 405.4 mmol, 2.2 equiv) in CH2Cl2 (600 ml). A solution of (2-hydroxymethyl-6-methoxy-phenyl)-methanol (30.97 g, 184.3 mmol) in CH2Cl2 (250 ml) was added dropwise, while maintaining the temperature of the reaction mixture below −68° C. 90 minutes after completed addition, triethylamine (335.65 g, 3.317 mol, 18 equiv) was slowly added at −78° C. The reaction mixture was warmed to room temperature over 2 hours, at which point TLC analysis indicated complete conversion. Water (500 ml) was added, and the mixture was extracted with CH2Cl2 (4 liters in total). The combined organic layers were dried over Na2SO4, filtered and concentrated in vacuo. Purification of the residue via flash chromatography (gradient of hexane/EtOAc 100:0 to 0:100) afforded 28.78 g of a orange-brown solid, which was recrystallized from CH2Cl2/hexane to give a first crop of pure title compound (brown solid, 9.68 g). Further purification of the mother liquor via flash chromatography and recrystallization afforded another 7.95 g of pure title compound (total: 17.63 g, 58%). 1H NMR (400 MHz, CDCl3): δ=10.64 (s, 1H), 10.42 (s, 1H), 7.64 (t, J=7.9 Hz, 1H), 7.44 (d, J=7.8 Hz, 1H), 7.23 (dd, J=8.5/0.9 Hz, 1H), 3.97 (s, 3H). MS (ES+): 165 (M+H)+.

後処理

  1. temperaturewhile maintaining the temperature of the reaction mixture below −68° C
  2. custom90 minutes
  3. additionwas slowly added at −78° C
  4. extractionthe mixture was extracted with CH2Cl2 (4 liters in total)
  5. dry with materialThe combined organic layers were dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated in vacuo
  8. customPurification of the residue via flash chromatography (gradient of hexane/EtOAc 100:0 to 0:100)

出典と根拠

ORDレコード
ord-20e81b8bbc1e4df6a613a82b88d065e8
出典データセット
uspto-grants-2010_08
特許番号
US07781438B2

反応ノート

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