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

HRID 1370202노트

반응식

HRID 1370202 반응식
[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]

참가 물질

7

반응물 4

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

생성물 1

HCID 187608894-(2,2-Diethoxyethoxy)benzaldehyde수율 79%

시약·촉매·용매 2

HCID 74236Tetrabutylammonium Bromide촉매HCID 962Water용매

실험 절차

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.

후처리

  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)

출처 및 근거

ORD 기록
ord-fb4dcae5aa8e4d7b9e20264c1074210e
출처 데이터셋
uspto-grants-2003_06
특허 번호
US06583140B2

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