Cesium carbonate → 1-(Dimethyl-phosphinoyl)-4-nitro-benzene

HRID 511216Notes

Reaction equation

HRID 511216 reaction equation
I[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1.[CH3:11][PH:12](=[O:14])[CH3:13].C([O-])([O-])=O.[Cs+].[Cs+]>O1CCOCC1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].CC1(C)C2C(=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=CC=2)OC2C(P(C3C=CC=CC=3)C3C=CC=CC=3)=CC=CC1=2>[CH3:11][P:12](=[O:14])([CH3:13])[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[CH:4][CH:3]=1

Participants

7

Reactant 3

HCID 10796Cesium carbonateHCID 124951-Iodo-4-nitrobenzeneHCID 178503022methylphosphonoylmethane

Product 1

HCID 218979121-(Dimethyl-phosphinoyl)-4-nitro-benzeneYield 36.3%

Reagents, catalysts & solvents 3

HCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)CatalystHCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
90 °C

Procedure

A degassed suspension of 1-iodo-4-nitrobenzene (90 mg, 0.36 mmol), dimethylphosphane oxide (29.2 mg, 0.38 mmol), bis(dibenzylideneacetone)palladium (3.31 mg, 0.0036 mmol), XantPhos (6.27 mg, 0.0108 mmol), and Cs2CO3 (165 mg, 0.506 mmol) in dry dioxane (0.4 mL) was heated in a sealed tube at 90° C. for 4 h. The cooled mixture was filtered, the filtrate concentrated in vacuo, and the residue chromatographed over silica gel eluting with 5% MeOH in dichloromethane to afford 26 mg of dimethyl(4-nitrophenyl)phosphane oxide (yield: 36%).

Workup

  1. filtrationThe cooled mixture was filtered
  2. concentrationthe filtrate concentrated in vacuo
  3. customthe residue chromatographed over silica gel eluting with 5% MeOH in dichloromethane

Sources & evidence

ORD record
ord-888e2891d838492ab0fee53c43e5e966
Source dataset
uspto-grants-2015_08
Patent number
US09096624B2

Reaction notes

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