Potassium Phosphate, Tribasic → Tert-butyl 4-[cyano(diethoxyphosphoryl)methyl]benzoate

HRID 1013466Notes

Reaction equation

HRID 1013466 reaction equation
[C:1]([CH2:3][P:4](=[O:11])([O:8][CH2:9][CH3:10])[O:5][CH2:6][CH3:7])#[N:2].Br[C:13]1[CH:25]=[CH:24][C:16]([C:17]([O:19][C:20]([CH3:23])([CH3:22])[CH3:21])=[O:18])=[CH:15][CH:14]=1.P([O-])([O-])([O-])=O.[K+].[K+].[K+]>CC(C)([P](C(C)(C)C)([Pd][P](C(C)(C)C)(C(C)(C)C)C(C)(C)C)C(C)(C)C)C.C1(C)C=CC=CC=1>[C:1]([CH:3]([P:4]([O:8][CH2:9][CH3:10])([O:5][CH2:6][CH3:7])=[O:11])[C:13]1[CH:25]=[CH:24][C:16]([C:17]([O:19][C:20]([CH3:21])([CH3:22])[CH3:23])=[O:18])=[CH:15][CH:14]=1)#[N:2]

Participants

6

Reactant 3

HCID 62657Potassium Phosphate, TribasicHCID 75676Diethyl (cyanomethyl)phosphonateHCID 11334366Tert-butyl 4-bromobenzoate

Product 1

HCID 57925819Tert-butyl 4-[cyano(diethoxyphosphoryl)methyl]benzoate

Reagents, catalysts & solvents 2

HCID 178418851HCID 178418851, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

Diethyl cyanomethylphosphonate (0.35 ml, 2.164 mmol), tert-butyl 4-bromobenzoate (0.5096 g, 1.982 mmol), bis(tri-t-butylphosphine)palladium (0.051 g, 0.099 mmol), potassium phosphate, tribasic (1.2381 g, 5.83 mmol) and toluene (6 ml) were combined in a flask. Nitrogen was bubbled through the reaction for approximately two minutes to deoxygenate the reaction. The reaction was allowed to heat at 100° C. until complete (3-24 h). The reaction was filtered over celite. The resulting material was partially purified by column chromatography on silica gel. The partially purified material was further purified by HPLC. 1H NMR (CDCl3, 600 MHz) δ 8.01 (d, J=6 Hz, 2H), 7.52 (d, J=6.9 Hz, 2H), 4.30 (d, JP-H=26.4 Hz, 1H), 4.19-4.01 (m, 4H), 1.59 (s, 9H), 1.32 (m, 3H), 1.26 (m, 3H). MS: cal'd 354 (MH+), exp 354 (MH+).

Workup

  1. customNitrogen was bubbled through the reaction for approximately two minutes
  2. customto deoxygenate
  3. customthe reaction
  4. filtrationThe reaction was filtered over celite
  5. customThe resulting material was partially purified by column chromatography on silica gel
  6. customThe partially purified material was further purified by HPLC

Sources & evidence

ORD record
ord-7f14e3f469ea498c94bcbb1c5d65fef8
Source dataset
uspto-grants-2011_07
Patent number
US07981874B2

Reaction notes

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