Cesium carbonate → N-benzyl-5-phenyl-2-vinylpyrrolo[2,1-f][1,2,4]triazin-4-amine

HRID 2170165Notes

Reaction equation

HRID 2170165 reaction equation
[CH2:1]([NH:8][C:9]1[C:14]2=[C:15]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[CH:16]=[CH:17][N:13]2[N:12]=[C:11](Cl)[N:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.B1(C=C)OB([CH:31]=[CH2:32])OB(C=C)O1.C1C=CN=CC=1.C(=O)([O-])[O-].[Cs+].[Cs+]>O1CCOCC1.O>[CH2:1]([NH:8][C:9]1[C:14]2=[C:15]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[CH:16]=[CH:17][N:13]2[N:12]=[C:11]([CH:31]=[CH2:32])[N:10]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1

Participants

6

Reactant 3

HCID 10796Cesium carbonateHCID 27348062,4,6-Trivinylboroxin-Pyridine ComplexHCID 90386076N-benzyl-2-chloro-5-phenylpyrrolo[2,1-f][1,2,4]triazin-4-amine

Product 1

HCID 90386136N-benzyl-5-phenyl-2-vinylpyrrolo[2,1-f][1,2,4]triazin-4-amineYield 68.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
110 °C

Procedure

N-Benzyl-2-chloro-5-phenylpyrrolo[2,1-f][1,2,4]triazin-4-amine (0.300 g, 0.896 mmol) (as in Example 4) and 2,4,6-trivinyl cyclotriboroxane pyridine complex (0.323 g, 1.34 mmol) were dissolved in dioxane (15 mL) and then cesium carbonate (0.584 g, 1.79 mmol) dissolved in water (2 mL) was added. The reaction mixture was degassed with nitrogen for 15 minutes, then tetrakistriphenylphosphine palladium (0.0520 g, 0.0450 mmol) was added and the resulting reaction mixture degassed for 15 minutes. The reaction mixture was then heated to 110° C. for 14 h, allowed to cool, concentrated under reduced pressure and CH2Cl2 (25 mL) was added. The residue was filtered through a CELITE® bed and the filterate dried over sodium sulfate, filtered and concentrated under reduced pressure. The residue was purified by column chromatography using CombiFlash (REDISEP®, silica gel, 24 g, 3% methanol in chloroform) to yield N-benzyl-5-phenyl-2-vinylpyrrolo[2,1-f][1,2,4]triazin-4-amine (0.200 g, 34.2%). LCMS Condition B-25: retention time 3.12 min, [M+1]=327.2. 1H NMR (400 MHz, DMSO-d6) δ ppm 4.72 (d, J=5.6 Hz, 2H), 5.60 (d, J=2.4 Hz, J=10.4 Hz, 1H), 6.36-6.56 (m, 3H), 6.72 (d, J=2.8 Hz, 1H), 7.30-7.37 (m, 5H), 7.42-7.52 (m, 5H), 7.74 (d, J=2.8 Hz, 1H).

Workup

  1. additionwas added
  2. customThe reaction mixture was degassed with nitrogen for 15 minutes
  3. customthe resulting reaction mixture
  4. customdegassed for 15 minutes
  5. temperatureto cool
  6. concentrationconcentrated under reduced pressure and CH2Cl2 (25 mL)
  7. additionwas added
  8. filtrationThe residue was filtered through a CELITE® bed
  9. dry with materialthe filterate dried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated under reduced pressure
  12. customThe residue was purified by column chromatography

Sources & evidence

ORD record
ord-50771f8a6f4b44cab25b2e7217a07bda
Source dataset
uspto-grants-2015_06
Patent number
US09050345B2

Reaction notes

Loading…