Tetrabutylammonium Fluoride → 4-[6-ethynyl-2-(oxetan-3-yloxy)-1H-1,3-benzodiazol-1-yl]pyrimidin-2-amine

HRID 1398685Notes

Reaction equation

HRID 1398685 reaction equation
[O:1]1[CH2:4][CH:3]([O:5][C:6]2[N:10]([C:11]3[CH:16]=[CH:15][N:14]=[C:13]([NH2:17])[N:12]=3)[C:9]3[CH:18]=[C:19]([C:22]#[C:23][Si](C)(C)C)[CH:20]=[CH:21][C:8]=3[N:7]=2)[CH2:2]1.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1>[C:22]([C:19]1[CH:20]=[CH:21][C:8]2[N:7]=[C:6]([O:5][CH:3]3[CH2:2][O:1][CH2:4]3)[N:10]([C:11]3[CH:16]=[CH:15][N:14]=[C:13]([NH2:17])[N:12]=3)[C:9]=2[CH:18]=1)#[CH:23]

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 681818264-[2-(oxetan-3-yloxy)-6-[2-(trimethylsilyl)ethynyl]-1H-1,3-benzodiazol-1-yl]pyrimidin-2-amine

Product 1

HCID 866696124-[6-ethynyl-2-(oxetan-3-yloxy)-1H-1,3-benzodiazol-1-yl]pyrimidin-2-amine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

To a solution of 4-[2-(oxetan-3-yloxy)-6-[2-(trimethylsilyl)ethynyl]-1H-1,3-benzodiazol-1-yl]pyrimidin-2-amine (450 mg, 1.19 mmol) in dry THF (5 mL) at RT was introduced TBAF (0.88 mL of a 1M solution in THF, 0.88 mmol). After 20 minutes, the reaction mixture was concentrated in vacuo, DCM (5 mL) added and the solution re-evaporated to dryness in vacuo (re-evaporation process repeated twice). Purification of the residue by silica gel flash column chromatography (eluent: DCM containing a 2-10% gradient of methanol) furnished the title compound as a yellow solid: 1H (500 MHz, DMSO) delta 4.83-4.70 (2H, m), 5.04-4.93 (2H, m), 5.85-5.77 (1H, m), 7.18-7.07 (3H, m), 7.33 (1H, dd, J=8.2, 1.5 Hz), 7.45 (1H, d, J=8.2 Hz), 8.36 (1H, s), 8.40 (1H, d, J=5.5 Hz); LCMS: m/z=+307.95 (M+H)+.

Workup

  1. concentrationthe reaction mixture was concentrated in vacuo, DCM (5 mL)
  2. additionadded
  3. customthe solution re-evaporated to dryness in vacuo (
  4. customre-evaporation process
  5. customPurification of the residue by silica gel flash column chromatography (eluent

Sources & evidence

ORD record
ord-7975485592684f5f99fbbdfe5e4c82bb
Source dataset
uspto-grants-2014_12
Patent number
US08901313B2

Reaction notes

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