Triphenylphosphine → 4-Methoxy-3-(2-morpholin-4-yl-ethoxy)benzoic acid methyl ester

HRID 1983576Notes

Reaction equation

HRID 1983576 reaction equation
[OH:1][C:2]1[CH:3]=[C:4]([CH:9]=[CH:10][C:11]=1[O:12][CH3:13])[C:5]([O:7][CH3:8])=[O:6].O[CH2:15][CH2:16][N:17]1[CH2:22][CH2:21][O:20][CH2:19][CH2:18]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OCC)=O)=NC(OCC)=O.N(C(OCC)=O)(C(OCC)=O)N>C(OCC)(=O)C>[CH3:8][O:7][C:5](=[O:6])[C:4]1[CH:9]=[CH:10][C:11]([O:12][CH3:13])=[C:2]([O:1][CH2:15][CH2:16][N:17]2[CH2:22][CH2:21][O:20][CH2:19][CH2:18]2)[CH:3]=1

Participants

7

Reactant 5

HCID 11776TriphenylphosphineHCID 611632-MorpholinoethanolHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 4056967Methyl 3-hydroxy-4-methoxybenzoateHCID 12066737Diethyl hydrazinedicarboxylate

Product 1

HCID 688435604-Methoxy-3-(2-morpholin-4-yl-ethoxy)benzoic acid methyl ester

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent2×

Procedure

To stirred solution of methyl 3-hydroxy-4-methoxybenzoate (2.00 g, 11.0 mmol), 4-(2-hydroxyethyl)morpholine (1.58 g, 12.0 mmol) and triphenylphosphine (3.17 g, 12.1 mmol) in ethyl acetate (60 mL) was added, dropwise, diethyl azodicarboxylate (1.9 mL, 12.1 mmol). The reaction was allowed to proceed overnight and then diluted with additional ethyl acetate and extracted with 1 N aqueous hydrochloric acid. The aqueous layer was washed with ethyl acetate, basified with concentrated ammonium hydroxide and then extracted with ethyl acetate. The organic extract was dried (sodium sulfate) and concentrated to afford 3.25 g of a 92:8 mixture of product (95%) and diethyl hydrazinedicarboxylate as an amber oil. This material was used without further purification in the next step: 1H NMR (CDCl3) δ 7.69 (dd, J=8.4, 2.0 Hz, 1H), 7.58 (d, J=2.0 Hz, 1H), 6.89 (d, J=8.4 Hz, 1H), 4.20 (t, J=6.0 Hz, 2H), 3.91 (s, 3H), 3.89 (s, 3H), 3.77-3.72 (m, 4H), 2.87 (t, J=6.0 Hz, 2H), 2.65-2.57 (m, 4H) ppm.

Workup

  1. additionwas added
  2. extractionextracted with 1 N aqueous hydrochloric acid
  3. washThe aqueous layer was washed with ethyl acetate
  4. extractionextracted with ethyl acetate
  5. extractionThe organic extract
  6. dry with materialwas dried (sodium sulfate)
  7. concentrationconcentrated
  8. customto afford
  9. customThis material was used without further purification in the next step

Sources & evidence

ORD record
ord-3e955c7668fb4e7ebce22aafbefa51bf
Source dataset
uspto-grants-2009_06
Patent number
US07541466B2

Reaction notes

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