Diethyl Ether → HCID 58307292, compound

HRID 448321Notes

Reaction equation

HRID 448321 reaction equation
[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:5](=[C:10](Br)[CH:11]=[CH:12][CH:13]=1)[C:6]([O:8][CH3:9])=[O:7].C([O-])([O-])=O.[Cs+].[Cs+].[CH3:22][O:23][CH2:24][CH:25]([NH2:27])[CH3:26].C(OCC)C>C1(C)C=CC=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.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd]>[CH3:1][O:2][C:3](=[O:15])[C:4]1[C:5](=[C:10]([NH:27][CH:25]([CH3:26])[CH2:24][O:23][CH3:22])[CH:11]=[CH:12][CH:13]=1)[C:6]([O:8][CH3:9])=[O:7]

Participants

7

Reactant 4

HCID 3283Diethyl EtherHCID 10796Cesium carbonateHCID 123458MethoxyisopropylamineHCID 53438518Dimethyl 3-bromobenzene-1,2-dicarboxylate

Product 1

HCID 58307292HCID 58307292, compoundYield 38%

Reagents, catalysts & solvents 2

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolvent

Procedure

To a stirred solution of 3-Bromophthalic acid dimethyl ester (0.82 g, 3.0 mmol) in toluene (20 mL), were added S-BINAP (56 mg, 0.09 mmol), Pd2(dba)3 (55 mg, 0.06 mmol), Cs2CO3 (1.37 g, 4.2 mmol), and 1-methoxy-2-propanamine (0.32 g, 3.6 mmol), and the resulting mixture was heated to reflux with stirring under nitrogen for 24 hours. The mixture was allowed to cool to room temperature, and diethyl ether was added (70 mL). The mixture was filtered, and the filtrate was evaporated in vacuo. The residue was chromatographed eluting with 17:3 hexanes-ethyl acetate. The resulting material was further purified by preparative HPLC, eluting with 11:9 water-acetonitrile, and providing 0.32 g of the product in 38% yield: 1H NMR (DMSO-d6) δ1.14 (d, J=6.4 Hz, 3H), 3.29 (s, 3H), 3.37 (d, J=4.8 Hz, 2H), 3.74 (s, 3H), 3.77 (s, 3H), 3.74-3.80 (m, 1H), 6.53 (d, J=7.8 Hz, 1H), 6.76 (d, J=7.3 Hz, 1H), 6.99 (d, J=8.6 Hz, 1H), 7.38 (t, J=7.8 Hz, 1H).

Workup

  1. temperaturethe resulting mixture was heated
  2. temperatureto reflux
  3. filtrationThe mixture was filtered
  4. customthe filtrate was evaporated in vacuo
  5. customThe residue was chromatographed
  6. washeluting with 17:3 hexanes-ethyl acetate
  7. customThe resulting material was further purified by preparative HPLC
  8. washeluting with 11:9 water-acetonitrile

Sources & evidence

ORD record
ord-870a0029f3b84030b8f2cd1b9c5679f8
Source dataset
uspto-grants-2013_07
Patent number
US08481568B2

Reaction notes

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