Hexamethylphosphorous triamide → 2-(4-Bromo-1H-pyrazolo[3,4-d]pyrimidin-1-yl)-1-phenylethanol

HRID 732935Notes

Reaction equation

HRID 732935 reaction equation
[OH:1][CH:2]([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)[CH2:3][N:4]1[C:8]2[N:9]=[CH:10][NH:11][C:12](=O)[C:7]=2[CH:6]=[N:5]1.C1C(=O)N([Br:27])C(=O)C1.CN(C)P(N(C)C)N(C)C.[Li+].[Br-]>C(#N)C>[Br:27][C:12]1[N:11]=[CH:10][N:9]=[C:8]2[N:4]([CH2:3][CH:2]([C:14]3[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=3)[OH:1])[N:5]=[CH:6][C:7]=12

Participants

6

Reactant 4

HCID 15355Hexamethylphosphorous triamideHCID 67184N-bromobutanimideHCID 82050Lithium BromideHCID 1363835291-(2-Hydroxy-2-phenylethyl)-1,5-dihydro-4H-pyrazolo[3,4-d]pyrimidin-4-one

Product 1

HCID 866099072-(4-Bromo-1H-pyrazolo[3,4-d]pyrimidin-1-yl)-1-phenylethanolYield 44%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Procedure

To a cold (−20° C.) suspension of 10 (2.56 g, 10 mmol) and NBS (7.12 g, 40 mmol) in dry acetonitrile (20 mL), hexamethylphosphorous triamide (HT) (6.53 g, 40 mmol) was added dropwise. After addition, the cold bath was removed and the reaction mixture stirred at room temperature for 0.5 h. LiBr (3.44 g, 40 mmol) was added and the mixture was heated at 70° C. for 5 h. The mixture was evaporated under reduced pressure. The dark oil was purified by column chromatography (Silica Gel, 100 Mesh) using CHCl3 as the eluant, to afford the pure product 11 (1.40 g, 44%) as a white solid: mp 146-147° C. 1H NMR: δ 3.46-3.53 (br s, 1H, OH, disappears with D2O), 4.57-4.79 (m, 2H, CH2N), 5.18-5.29 (m, 1H, CHO), 7.30-7.52 (m, 5H Ar), 8.01 (s, 1H, H-3), 8.48 (s, 1H, H-6). IR cm−1: 3240-2500 (OH). Anal. (C13H11N4OBr) C, H, N.

Workup

  1. additionwas added dropwise
  2. additionAfter addition
  3. customthe cold bath was removed
  4. temperaturethe mixture was heated at 70° C. for 5 h
  5. customThe mixture was evaporated under reduced pressure
  6. customThe dark oil was purified by column chromatography (Silica Gel, 100 Mesh)

Sources & evidence

ORD record
ord-826e3ce6599a413d8415ff5701803048
Source dataset
uspto-grants-2009_09
Patent number
US07589086B2

Reaction notes

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