Triphenylphosphine → 2-Chlorobenzenesulfonic acid 3-[(3-cyanophenyl)methoxy]-5-methylphenyl ester

HRID 1976086Notes

Reaction equation

HRID 1976086 reaction equation
N(C(OCC)=O)=NC(OCC)=O.[OH:13][C:14]1[CH:15]=[C:16]([O:21][S:22]([C:25]2[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=2[Cl:31])(=[O:24])=[O:23])[CH:17]=[C:18]([CH3:20])[CH:19]=1.[C:32]([C:34]1[CH:35]=[C:36]([CH:39]=[CH:40][CH:41]=1)[CH2:37]O)#[N:33].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>O1CCCC1>[C:32]([C:34]1[CH:35]=[C:36]([CH2:37][O:13][C:14]2[CH:15]=[C:16]([O:21][S:22]([C:25]3[CH:30]=[CH:29][CH:28]=[CH:27][C:26]=3[Cl:31])(=[O:24])=[O:23])[CH:17]=[C:18]([CH3:20])[CH:19]=2)[CH:39]=[CH:40][CH:41]=1)#[N:33]

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 220568ethyl N-ethoxycarbonyliminocarbamateHCID 27346773-(Hydroxymethyl)benzonitrileHCID 112779473-(2-Chlorophenylsulfonyloxy)-5-methylphenol

Product 1

HCID 540597372-Chlorobenzenesulfonic acid 3-[(3-cyanophenyl)methoxy]-5-methylphenyl esterYield 89%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

Diethyl azodicarboxylate (349 mg, 2.0 mmol) was added to a solution of 2-chlorobenzenesulfonic acid 3-hydroxy-5-methylphenyl ester (900 mg, 3.0 mmol), as prepared in step (c) of Example 1, 3-cyanobenzyl alcohol (400 mg, 3.0 mmol; Yoon et al., J. Org. Chem. 38:2786-2792 (1973)), and triphenylphosphine (525 mg, 2.0 mmol) in tetrahydrofuran (20 mL) at 0° C. The mixture was stirred at 0° C. for 2 h and at room temperature for 3 h. The reaction mixture was quenched with water (50 mL) and extracted with ethyl acetate (3×50 mL). The organic phase was washed with saturated NaHCO3 (2×50 mL), brine (2×50 mL) and dried over Na2SO4. The solvent was removed in vacuo and the residue was purified by flash column chromatography (2:1 ethyl acetate/hexane) to give the title compound as a white solid (1.10 g, 89%). 1H-NMR (300 MHz, CDCl3) δ 2.26 (s, 3 H), 4.99 (s, 2 H), 6.55 (t, 1 H, J=2.3 Hz), 6.60 (t, 1 H, J=0.7 Hz), 6.67 (t, 1 H, J=0.7 Hz), 7.39 (m, 1 H), 7.50 (t, 1 H, J=7.7 Hz), 7.61 (m, 5 H), and 7.96 (d, 1 H, J=1.3 Hz).

Workup

  1. customThe reaction mixture was quenched with water (50 mL)
  2. extractionextracted with ethyl acetate (3×50 mL)
  3. washThe organic phase was washed with saturated NaHCO3 (2×50 mL), brine (2×50 mL)
  4. dry with materialdried over Na2SO4
  5. customThe solvent was removed in vacuo
  6. customthe residue was purified by flash column chromatography (2:1 ethyl acetate/hexane)

Sources & evidence

ORD record
ord-10ca5fb91fae43b683dd4ed8b0e6f5b3
Source dataset
uspto-grants-2001_05
Patent number
US06225302B1

Reaction notes

Loading…