Triphenylphosphine → HCID 23512311, compound

HRID 354478Notes

Reaction equation

HRID 354478 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:11]=[CH:12][C:13]=1[OH:14])[C:7]([O:9][CH3:10])=[O:8])([O-:3])=[O:2].C([NH:22][CH2:23][CH2:24]O)(OC(C)(C)C)=O.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1.C(Cl)Cl>[N+:1]([C:4]1[CH:5]=[C:6]([CH:11]=[CH:12][C:13]=1[O:14][CH2:24][CH2:23][NH2:22])[C:7]([O:9][CH3:10])=[O:8])([O-:3])=[O:2]

Participants

7

Reactant 4

HCID 11776TriphenylphosphineHCID 66835Benzoic acid, 4-hydroxy-3-nitro-, methyl esterHCID 2733206tert-butyl N-(2-hydroxyethyl)carbamateHCID 5363146Diisopropyl azodicarboxylate

Product 1

HCID 23512311HCID 23512311, compoundYield 38.6%

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a stirred solution of methyl 3-nitro-4-hydroxybenzoate (1.98 g, 10.04 mmol), N-Boc ethanolamine (1.63 g, 10.11 mmol) and PPh3 (3.43 g, 13.08 mmol) in THF (40 mL) was added DIAD (2.57 mL, 13.05 mmol), and the reaction mixture was then heated under reflux overnight. The resulting mixture was evaporated to give a gum. The residual crude gum was dissolved in CH2Cl2 (30 mL) and TEA (30 mL), and the mixture was stirred for 1 hr at room temp. The mixture was concentrated in vacuo and made basic with sat. NaHCO3. The mixture was extracted with CHCl3, washed with brine, and dried over Na2SO4. The solvent was evaporated in vacuo to give the oily residue, which was purified by column chromatography on silica-gel with CHCl3 then CHCl3—MeOH (20:1, v/v) as eluent to give 930 mg (27% for 2 steps ) methyl 3-nitro-4-(2-aminoethoxy)benzoate as gum. 1H-NMR (CDCl3) d 3.16-3.19 (m, 1 H), 3.53-3.57 (m, 1 H), 3.90 and 3.94 (s, 3 H), 3.95-3.98 (m, 1 H), 4.21-4.24 (m, 1 H), 6.89-6.91 and 7.11-7.13 (m, 1 H), 8.03-8.19 and 8.21 (m, 1 H), 8.52 and 8.86 (m, 1 H).

Workup

  1. temperaturethe reaction mixture was then heated
  2. temperatureunder reflux overnight
  3. customThe resulting mixture was evaporated
  4. customto give a gum
  5. concentrationThe mixture was concentrated in vacuo
  6. extractionThe mixture was extracted with CHCl3
  7. washwashed with brine
  8. dry with materialdried over Na2SO4
  9. customThe solvent was evaporated in vacuo
  10. customto give the oily residue, which
  11. customwas purified by column chromatography on silica-gel with CHCl3

Sources & evidence

ORD record
ord-0c799ea125af486f8187552fad288db3
Source dataset
uspto-grants-2004_06
Patent number
US06756378B2

Reaction notes

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