4-Hydroxybenzaldehyde → 4-(2,2-Diethoxyethoxy)benzaldehyde

HRID 1370202ノート

反応式

HRID 1370202 の反応式
[OH:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1.C([CH:12](CC)[C:13]([OH:15])=[O:14])C.Br[CH2:19][CH:20]=O.C(=O)([O-])[O-].[K+].[K+].[C:28]1(C)C=CC=C[CH:29]=1>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.O>[CH2:28]([O:15][CH:13]([O:14][CH2:19][CH3:20])[CH2:12][O:1][C:2]1[CH:9]=[CH:8][C:5]([CH:6]=[O:7])=[CH:4][CH:3]=1)[CH3:29]

参加物

7

反応物 4

HCID 1264-HydroxybenzaldehydeHCID 1140TolueneHCID 11430Potassium CarbonateHCID 86586421Bromoacetaldehyde diethyl acetate

生成物 1

HCID 187608894-(2,2-Diethoxyethoxy)benzaldehyde収率 79%

試薬・触媒・溶媒 2

HCID 74236Tetrabutylammonium Bromide触媒HCID 962Water溶媒

実験手順

Under nitrogen, a mixture of 4-hydroxybenzaldehyde (1.71 g, 14 mmol), bromoacetaldehyde diethyl acetate (37.4 g, 190 mmol), tetrabutylammonium bromide (0.61 g, 1.9 mmol) and potassium carbonate (26.1 g, 190 mmol) in 100 mL of toluene was refluxed for 2.5 days. After cooling the mixture was dissolved in water and extracted with dichloromethane. The organic layers were dried over magnesium sulfate and concentrated. The residue was purified by column chromatography (eluent: hexanes/ethyl acetate) to give 4-(2,2-diethoxyethoxy) benzaldehyde as a colorless oil (2.60 g, 79%). The title compound was prepared from 4-(2,2-diethoxyethoxy) benzaldehyde and rhodanine according to the procedure of Intermediate 15 as a yellowish solid; 1H NMR (300 MHz, DMSO-d6) δ 1.14(t, J=7.1 Hz, 6 H), 3.50-3.80 (m, 4 H), 4.04(d, J=5.0 Hz, 2 H), 4.05-4.30(m, 2 H), 6.06 (t, J=5.0 Hz, 1 H), 7.14 (d, J=9.0 Hz, 2 H), 7.60 (d, J=9.0 Hz, 2 H), 7.63(s, 1 H); MS (ES) m/z:351.7 ((M−H)−, 100%); HRMS Calcd. for C16H20NO4S2 (MH+): 353.0775. Found: 353.0757.

後処理

  1. temperaturewas refluxed for 2.5 days
  2. temperatureAfter cooling the mixture
  3. extractionextracted with dichloromethane
  4. dry with materialThe organic layers were dried over magnesium sulfate
  5. concentrationconcentrated
  6. customThe residue was purified by column chromatography (eluent: hexanes/ethyl acetate)

出典と根拠

ORDレコード
ord-fb4dcae5aa8e4d7b9e20264c1074210e
出典データセット
uspto-grants-2003_06
特許番号
US06583140B2

反応ノート

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