Cesium carbonate → 4-(4-Methyl-1,4-diazepan-1-yl)-2-(propan-2-yloxy)nitrobenzene

HRID 518880Notes

Reaction equation

HRID 518880 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([O:11][CH:12]([CH3:14])[CH3:13])[CH:3]=1.C(=O)([O-])[O-].[Cs+].[Cs+].[CH3:21][N:22]1[CH2:28][CH2:27][CH2:26][NH:25][CH2:24][CH2:23]1.CC1(C)C2C=CC=C(P(C3C=CC=CC=3)C3C=CC=CC=3)C=2OC2C1=CC=CC=2P(C1C=CC=CC=1)C1C=CC=CC=1>O1CCOCC1.C(OCC)(=O)C.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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:21][N:22]1[CH2:28][CH2:27][CH2:26][N:25]([C:2]2[CH:7]=[CH:6][C:5]([N+:8]([O-:10])=[O:9])=[C:4]([O:11][CH:12]([CH3:14])[CH3:13])[CH:3]=2)[CH2:24][CH2:23]1

Participants

8

Reactant 4

HCID 10796Cesium carbonateHCID 2283491-MethylhomopiperazineHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 226243214-Bromo-2-isopropoxy-1-nitro-benzene

Product 1

HCID 866980294-(4-Methyl-1,4-diazepan-1-yl)-2-(propan-2-yloxy)nitrobenzeneYield 39%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8857Ethyl AcetateSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
150 °C

Procedure

A mixture of 250 mg of 4-bromo-1-nitro-2-(propan-2-yloxy)benzene, 1.13 g of caesium carbonate, 197 mg of N-methylhomopiperazine, 47.5 mg of tris(dibenzylideneacetone)dipalladium(0) and 50 mg of 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene in 5 ml of 1,4-dioxane is microwave-heated in a sealed tube, at 150° C. for 30 min, and then 200° C. for 10 min. The mixture is diluted with ethyl acetate and filtered on Clarcel. The Clarcel is washed with ethyl acetate and the organic phase is washed with water. The organic phase is dried over anhydrous magnesium sulfate, filtered and then concentrated to dryness under reduced pressure. The residue is purified on 12 g of silica, elution being carried out with 0-5% methanol in dichloromethane, so as to obtain 110 mg of 4-(4-methyl-1,4-diazepan-1-yl)-2-(propan-2-yloxy)nitrobenzene in the form of an orangey-coloured oil.

Workup

  1. filtrationfiltered on Clarcel
  2. washThe Clarcel is washed with ethyl acetate
  3. washthe organic phase is washed with water
  4. dry with materialThe organic phase is dried over anhydrous magnesium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated to dryness under reduced pressure
  7. customThe residue is purified on 12 g of silica, elution

Sources & evidence

ORD record
ord-14b1246a6620477da78bb403046a80bb
Source dataset
uspto-grants-2015_08
Patent number
US09115140B2

Reaction notes

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