Triethylamine → HCID 58528944, compound

HRID 1430992Notes

Reaction equation

HRID 1430992 reaction equation
[CH3:1][O:2][C:3](=[O:22])[C:4]1[CH:9]=[C:8]([O:10][CH:11]([CH3:13])[CH3:12])[CH:7]=[C:6]([O:14][C:15]2[CH:20]=[CH:19][C:18](Br)=[CH:17][CH:16]=2)[CH:5]=1.[P:23]([O-:32])([O:28][CH:29]([CH3:31])[CH3:30])[O:24][CH:25]([CH3:27])[CH3:26].C([SiH](CC)CC)C.CCN(CC)CC>C1(C)C=CC=CC=1.C1C=CC([PH+]([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C1C=CC([PH+]([C]2[CH][CH][CH][CH]2)C2C=CC=CC=2)=CC=1.C(Cl)Cl.Cl[Pd]Cl.[Fe].C(Cl)Cl>[CH3:1][O:2][C:3](=[O:22])[C:4]1[CH:9]=[C:8]([O:10][CH:11]([CH3:13])[CH3:12])[CH:7]=[C:6]([O:14][C:15]2[CH:20]=[CH:19][C:18]([P:23]([O:28][CH:29]([CH3:31])[CH3:30])([O:24][CH:25]([CH3:27])[CH3:26])=[O:32])=[CH:17][CH:16]=2)[CH:5]=1

Participants

8

Reactant 4

HCID 8471TriethylamineHCID 12052TriethylsilaneHCID 21884976Phosphorous acid, bis(1-methylethyl) esterHCID 58528801HCID 58528801, compound

Product 1

HCID 58528944HCID 58528944, compoundYield 65%

Reagents, catalysts & solvents 3

HCID 53485975CID 53485975CatalystHCID 1140TolueneSolventHCID 6344DichloromethaneSolvent

Conditions

Temperature
90 °C

Procedure

To a stirred solution of 3-(4-bromo-phenoxy)-5-isopropoxy-benzoic acid methyl ester (5.00 g) in toluene (120 mL) was added diisopropyl phosphite (2.80 mL), dichloro[1,1′-bis(diphenylphosphino)-ferrocene]palladium (II) dichloromethane adduct (1.00 g, 1.37 mmol), triethylsilane (0.44 mL, 2.74 mmol), and Et3N (5.72 mL, 41.1 mmol) at rt. DCM (12 mL) was added to the reaction flask which was purged with nitrogen. The mixture was heated at 90° C. overnight. Cooled to rt and concentrated. EtOAc and water were added and the mixture was filtered through a pad of Celite to remove the insoluble. The organic layer was separated, washed with brine (1×), dried with anhydrous MgSO4, filtered, and concentrated. The residue was purified by silica gel column (6×25 cm, hexane/EtOAc, v/v=5:1, 1:1). Fractions containing the product were pooled and concentrated to give 3-[4-(Diisopropoxy-phosphoryl)-phenoxy]-5-isopropoxy-benzoic acid methyl ester (4.0 g, 65%) as yellow oil. 1H NMR (300 MHz, CDCl3): δ 7.77 (dd, J=9, 13 Hz, 2H), 7.36 (dd, J=1, 2 Hz, 1H), 7.26 (m, 1H), 7.02 (dd, J=4, 9 Hz, 2H), 6.76 (dd, J=2, 2 Hz, 1H). 4.63-4.74 (m, 2H), 4.54-4.62 (m, 1H), 1.37 (d, J=6 Hz, 6H), 1.33 (d, J=6 Hz, 6H) 1.24 (d, J=6 Hz, 6H).

Workup

  1. customwas purged with nitrogen
  2. temperatureCooled to rt
  3. concentrationconcentrated
  4. additionEtOAc and water were added
  5. filtrationthe mixture was filtered through a pad of Celite
  6. customto remove the insoluble
  7. customThe organic layer was separated
  8. washwashed with brine (1×)
  9. dry with materialdried with anhydrous MgSO4
  10. filtrationfiltered
  11. concentrationconcentrated
  12. customThe residue was purified by silica gel column (6×25 cm, hexane/EtOAc, v/v=5:1, 1:1)
  13. additionFractions containing the product
  14. concentrationconcentrated

Sources & evidence

ORD record
ord-f250fef0223940d2b40faca195e9a1c6
Source dataset
uspto-grants-2015_01
Patent number
US08940927B2

Reaction notes

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