Cesium carbonate → HCID 53391274, compound

HRID 1045744Notes

Reaction equation

HRID 1045744 reaction equation
Br[C:2]1[N:7]2[N:8]=[N:9][N:10]=[C:6]2[C:5]([N:11]2[CH2:16][CH2:15][N:14]([CH3:17])[CH2:13][CH2:12]2)=[N:4][C:3]=1[CH3:18].[S:19]1[CH:23]=[CH:22][CH:21]=[C:20]1B(O)O.C([O-])([O-])=O.[Cs+].[Cs+].O1CCOCC1>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.O>[CH3:18][C:3]1[N:4]=[C:5]([N:11]2[CH2:16][CH2:15][N:14]([CH3:17])[CH2:13][CH2:12]2)[C:6]2[N:7]([N:8]=[N:9][N:10]=2)[C:2]=1[C:20]1[S:19][CH:23]=[CH:22][CH:21]=1

Participants

7

Reactant 4

HCID 10796Cesium carbonateHCID 312751,4-DioxaneHCID 27339602-Thiopheneboronic acidHCID 58447001HCID 58447001, compound

Product 1

HCID 53391274HCID 53391274, compoundYield 23%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolvent

Conditions

Temperature
100 °C

Procedure

A 50 mL round bottom flask was charged with 5-bromo-6-methyl-8-(4-methylpiperazin-1-yl)tetrazolo[1,5-a]pyrazine (0.72 g, 2.3 mmol), thiophene-2-boronic acid (0.46 g, 3.6 mmol), tetrakis(triphenylphosphine)palladium(0) (0.30 g, 0.26 mmol), Cs2CO3 (1.2 g, 3.7 mmol), 1,4-dioxane (12 mL) and water (6 mL). After the air was purged by bubbling N2 into the solution, the resulting mixture was stirred at 100° C. under N2 atmosphere overnight. Work-up: the reaction mixture was poured into 0.1 M HCl (40 mL) and washed with EtOAc (50 mL×2). The aqueous layer was then basified with solid NaHCO3 and extracted with CH2Cl2 (50 mL×3). The combined CH2Cl2 layers were dried over anhydrous Na2SO4 and concentrated in vacuo. The residue was purified by flash column chromatography on silica gel with 5% MeOH in CH2Cl2, to afford 165 mg (23%) of the product as a white solid. 1H NMR (300 MHz, CDCl3) δ: 7.59 (dd, J=5.1, 1.2 Hz, 1H), 7.38 (dd, J=3.6, 1.2 Hz, 1H), 7.21 (dd, J=5.1, 3.6 Hz, 1H), 4.40 (br, 4H), 2.60 (t, J=5.1 Hz, 4H), 2.47 (s, 3H), 2.38 (s, 3H). MS m/z: 316 (M+H+).

Workup

  1. customAfter the air was purged
  2. customby bubbling N2 into the solution
  3. additionthe reaction mixture was poured into 0.1 M HCl (40 mL)
  4. washwashed with EtOAc (50 mL×2)
  5. extractionextracted with CH2Cl2 (50 mL×3)
  6. dry with materialThe combined CH2Cl2 layers were dried over anhydrous Na2SO4
  7. concentrationconcentrated in vacuo
  8. customThe residue was purified by flash column chromatography on silica gel with 5% MeOH in CH2Cl2

Sources & evidence

ORD record
ord-2fbc3a446e394a4e8879b0d35b4404b3
Source dataset
uspto-grants-2013_10
Patent number
US08569300B2

Reaction notes

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