2-(Dimethylamino)ethanol → Ethyl 4-[2-(dimethylamino)ethoxy]-3-hydroxy-benzoate

HRID 131286

Reaction equation

HRID 131286 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([CH:10]=[CH:11][C:12]=1[OH:13])[C:5]([O:7][CH2:8][CH3:9])=[O:6].[CH3:14][N:15]([CH3:19])[CH2:16][CH2:17]O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>C(Cl)Cl.C(OCC)(=O)C>[CH3:14][N:15]([CH3:19])[CH2:16][CH2:17][O:13][C:12]1[CH:11]=[CH:10][C:4]([C:5]([O:7][CH2:8][CH3:9])=[O:6])=[CH:3][C:2]=1[OH:1]

Participants

7

Reactant 4

HCID 79022-(Dimethylamino)ethanolHCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 77547Ethyl 3,4-Dihydroxybenzoate

Product 1

HCID 69301243Ethyl 4-[2-(dimethylamino)ethoxy]-3-hydroxy-benzoateYield 35%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of ethyl 3,4-dihydroxybenzoate (500 mg), N,N-dimethylethanol-amine (565 μL), and triphenylphosphine (1.51 g) in methylene chloride (20 mL) is added dropwise diisopropyl azodicarboxylate (1.37 mL) under argon gas atmosphere and ice-cooling. The mixture is stirred at room temperature for 1 day. The reaction mixture is diluted with ethyl acetate, washed with water and treated with 10% HCl to transfer basic materials in ethyl acetate layer to the aqueous layer. The aqueous layer is neutralized with saturated aqueous sodium hydrogencarbonate and extracted with chloroform/methanol/tetrahydrofuran (4:1:1, ×2). The extract is dried over anhydrous sodium sulfate and concentrated in vacuo. The residue is purified by flash column chromatography on NH-silica gel (Solvent; n-hexane:ethyl acetate=1:1→chloroform:methanol=19:1) to give ethyl 4-[2-(dimethylamino)ethoxy]-3-hydroxy-benzoate (240 mg, yield; 35%) as oil. MS (APCI) m/z; 254 [M+H]+

Workup

  1. temperatureice-cooling
  2. washwashed with water
  3. additiontreated with 10% HCl
  4. extractionextracted with chloroform/methanol/tetrahydrofuran (4:1:1, ×2)
  5. dry with materialThe extract is dried over anhydrous sodium sulfate
  6. concentrationconcentrated in vacuo
  7. customThe residue is purified by flash column chromatography on NH-silica gel (Solvent; n-hexane:ethyl acetate=1:1→chloroform:methanol=19:1)

Sources & evidence

ORD record
ord-66c92dfc2c1c43d5a90d3461e73d3472
Source dataset
uspto-grants-2008_06
Patent number
US07384952B2

Linked notes

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