Cesium carbonate → 1-(2,2-Diethoxyethyl)-1'-(4-methoxybenzyl)-N-(2-methyl-5-nitrophenyl)-1H,1'H-3,4'-bipyrazole-5-amine

HRID 1055636Notes

Reaction equation

HRID 1055636 reaction equation
[CH2:1]([O:3][CH:4]([O:26][CH2:27][CH3:28])[CH2:5][N:6]1[C:10]([NH2:11])=[CH:9][C:8]([C:12]2[CH:13]=[N:14][N:15]([CH2:17][C:18]3[CH:23]=[CH:22][C:21]([O:24][CH3:25])=[CH:20][CH:19]=3)[CH:16]=2)=[N:7]1)[CH3:2].Br[C:30]1[CH:35]=[C:34]([N+:36]([O-:38])=[O:37])[CH:33]=[CH:32][C:31]=1[CH3:39].C(=O)([O-])[O-].[Cs+].[Cs+].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>O1CCOCC1.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[CH2:27]([O:26][CH:4]([O:3][CH2:1][CH3:2])[CH2:5][N:6]1[C:10]([NH:11][C:30]2[CH:35]=[C:34]([N+:36]([O-:38])=[O:37])[CH:33]=[CH:32][C:31]=2[CH3:39])=[CH:9][C:8]([C:12]2[CH:13]=[N:14][N:15]([CH2:17][C:18]3[CH:19]=[CH:20][C:21]([O:24][CH3:25])=[CH:22][CH:23]=3)[CH:16]=2)=[N:7]1)[CH3:28]

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 821892-Bromo-4-nitrotolueneHCID 6360441,1'-(9,9-Dimethyl-9H-xanthene-4,5-diyl)bis(1,1-diphenylphosphine)HCID 866909601-(2,2-Diethoxyethyl)-1'-(4-methoxybenzyl)-1H,1'H-3,4'-bipyrazol-5-amine

Product 1

HCID 866909591-(2,2-Diethoxyethyl)-1'-(4-methoxybenzyl)-N-(2-methyl-5-nitrophenyl)-1H,1'H-3,4'-bipyrazole-5-amine

Reagents, catalysts & solvents 2

HCID 167845palladium(II) acetateCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
150 °C

Procedure

Under argon, a mixture of the compound from Example 2A (2.9 g, 7.5 mmol), 2-bromo-4-nitrotoluene (2.11 g, 9.78 mmol), palladium(II) acetate (0.17 g, 0.75 mmol), caesium carbonate (4.90 g, 15.1 mmol) and xantphos (4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; 0.44 g, 0.75 mmol) in 37 ml of 1,4-dioxane was divided into several 20 ml-microwave reactor vessels. Each batch was heated in a single-mode microwave reactor (Biotage Emrys Optimizer) at 150° C. for 30 min. The batches were subsequently combined and filtered through kieselguhr, and the filtrate was concentrated on a rotary evaporator. The residue was taken up in ethyl acetate and washed with semiconcentrated sodium bicarbonate solution and then with concentrated sodium chloride solution. The organic phase was dried over anhydrous sodium sulphate and concentrated. The crude product was purified chromatographically (Method 26). This gave 2.74 g (70% of theory) of the title compound.

Workup

  1. filtrationfiltered through kieselguhr
  2. concentrationthe filtrate was concentrated on a rotary evaporator
  3. washwashed with semiconcentrated sodium bicarbonate solution
  4. dry with materialThe organic phase was dried over anhydrous sodium sulphate
  5. concentrationconcentrated
  6. customThe crude product was purified chromatographically (Method 26)

Sources & evidence

ORD record
ord-e166714936154cd2917807bc9e14ffd8
Source dataset
uspto-grants-2016_07
Patent number
US09394309B2

Reaction notes

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