1,3-Bis(diphenylphosphino)propane → 4-{3-[(Ethyloxy)(methyl)phosphoryl]propanoyl}benzoic acid

HRID 1013541Notes

Reaction equation

Br[C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:17])[CH2:9][CH2:10][P:11]([CH3:16])(=[O:15])[O:12][CH2:13][CH3:14])=[CH:4][CH:3]=1.C1(P(C2C=CC=CC=2)CCCP(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CCN(C(C)C)C(C)C.[C:56]([O-])([OH:58])=[O:57].[Na+]>CN(C=O)C.C([O-])(=O)C.[Pd+2].C([O-])(=O)C.O>[CH2:13]([O:12][P:11]([CH2:10][CH2:9][C:8]([C:5]1[CH:6]=[CH:7][C:2]([C:56]([OH:58])=[O:57])=[CH:3][CH:4]=1)=[O:17])([CH3:16])=[O:15])[CH3:14]

Participants

Conditions

Temperature: 70 °C

Procedure

Ethyl [3-(4-bromophenyl)-3-oxopropyl]methylphosphinate (3 g, 9.40 mmol), palladium(II) acetate (0.106 g, 0.470 mmol) and 1,3-bis(diphenylphosphino)propane (0.194 g, 0.470 mmol) were taken up in DMF (24 mL)/water (8 mL). CO was bubbled through for 10 minutes before adding DIPEA (3.28 mL, 18.80 mmol) and stirring at 70° C. under a balloon of CO overnight. Room temperature was attained and saturated NaHCO3 was added. The aqueous phase was extracted with EtOAc (×2) before acidifying with 2N HCl and extracting again with EtOAc (×2). The combined organic extracts from the acidic aqueous were washed with brine, dried over MgSO4 and concentrated in vacuo to give 4-{3-[(ethyloxy)(methyl)phosphoryl]propanoyl}benzoic acid as a pale yellow solid.

Workup

customCO was bubbled through for 10 minutes
customRoom temperature
extractionThe aqueous phase was extracted with EtOAc (×2)
extractionextracting again with EtOAc (×2)
washThe combined organic extracts from the acidic aqueous were washed with brine
dry with materialdried over MgSO4
concentrationconcentrated in vacuo

Sources & evidence

ORD record: ord-67a2db60404944e3b091552c87a3dbac
Source dataset: uspto-grants-2011_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07981874B2

Reaction notes

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