1,2-Dimethoxyethane → 1-Methyl-4-(2'-methyl-6-nitro-biphenyl-3-yl)-piperazine

HRID 2367762Notes

Reaction equation

HRID 2367762 reaction equation
Br[C:2]1[CH:3]=[C:4]([N:11]2[CH2:16][CH2:15][N:14]([CH3:17])[CH2:13][CH2:12]2)[CH:5]=[CH:6][C:7]=1[N+:8]([O-:10])=[O:9].C([O-])([O-])=O.[Na+].[Na+].[CH2:24]([CH2:27]OC)OC>C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH3:17][N:14]1[CH2:15][CH2:16][N:11]([C:4]2[CH:3]=[C:2]([C:4]3[CH:3]=[CH:2][CH:7]=[CH:6][C:24]=3[CH3:27])[C:7]([N+:8]([O-:10])=[O:9])=[CH:6][CH:5]=2)[CH2:12][CH2:13]1

Participants

5

Reactant 3

HCID 80711,2-DimethoxyethaneHCID 10340Sodium CarbonateHCID 117815411-(3-Bromo-4-nitrophenyl)-4-methylpiperazine

Product 1

HCID 591285961-Methyl-4-(2'-methyl-6-nitro-biphenyl-3-yl)-piperazine

Reagents, catalysts & solvents 1

HCID 178418397HCID 178418397, compoundCatalyst

Conditions

Temperature
80 °C

Procedure

A mixture of 200 mg (0.666 mmol) 1-(3-bromo-4-nitro-phenyl)-4-methyl-piperazine (as prepared in the previous step), 136 mg (0.999 mmol) and 77.0 mg (0.0666 mmol) of tetrakis(triphenylphosphine)palladium (0) under Ar was added 4.0 mL of degassed dimethoxyethane (DME) and 400 μL (0.799 mmol) of 2.0 M aq Na2CO3. The mixture was heated with stirring under Ar at 80° C. for 14 h. The cooled (RT) mixture was concentrated and chromatographed on a 10-g silica SPE column with 1-5% MeOH in dichloromethane-hexane (1:1). The product fractions were treated with 80 mg of decolorizing carbon, filtered, concentrated, and then rechromatographed on a similar column with 1-3% EtOH-dichloromethane to afford 265 mg of the title compound as a yellow resin (75% purity by 1H-NMR as a mixture with triphenylphosphine) that was used in the following reaction without further purification: Mass spectrum (ESI, m/z): Calcd. for C11H21N3O3, 312.2 (M+H). found 312.2.

Workup

  1. temperatureThe mixture was heated
  2. temperatureThe cooled (RT) mixture
  3. concentrationwas concentrated
  4. customchromatographed on a 10-g silica SPE column with 1-5% MeOH in dichloromethane-hexane (1:1)
  5. additionThe product fractions were treated with 80 mg of decolorizing carbon
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customrechromatographed on a similar column with 1-3% EtOH-dichloromethane

Sources & evidence

ORD record
ord-4d81ce98535c4692ae7be2009327851d
Source dataset
uspto-grants-2014_04
Patent number
US08697716B2

Reaction notes

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