Diisobutylaluminum hydride → HCID 22060456, compound

HRID 534567Notes

Reaction equation

HRID 534567 reaction equation
Cl[C:2]1([NH:24][C:25]2[CH:30]=[CH:29][C:28]3[O:31][CH2:32][CH2:33][O:34][C:27]=3[CH:26]=2)[N:7]=[C:6]([NH:8][C:9]2[CH:14]=[CH:13][C:12]([C:15]([C:18](OCC)=[O:19])([CH3:17])[CH3:16])=[CH:11][CH:10]=2)[C:5]([F:23])=[CH:4][NH:3]1.CC(C[AlH]CC(C)C)C>ClCCl>[CH2:33]1[CH2:32][O:31][C:28]2[CH:29]=[CH:30][C:25]([NH:24][C:2]3[N:7]=[C:6]([NH:8][C:9]4[CH:14]=[CH:13][C:12]([C:15]([CH3:16])([CH3:17])[CH2:18][OH:19])=[CH:11][CH:10]=4)[C:5]([F:23])=[CH:4][N:3]=3)=[CH:26][C:27]=2[O:34]1

Participants

4

Reactant 2

HCID 14487Diisobutylaluminum hydrideHCID 178471260HCID 178471260, compound

Product 1

HCID 22060456HCID 22060456, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

2-Chloro-5-fluoro-N4-[4-[ethoxycarbonyl(dimethyl)methyl]phenyl]-N2-(3,4-ethylenedioxyphenyl)-2,4-pyrimidinediamine was reduced with 10 eq. DIBALH (1.0 M in toluene) at 0° C. in dichloromethane. Reaction was quenched with methanol, diluted with ethylacetate followed by the addition of aqueous Rochelle's salt solution, stirred at room temperature for 30 minutes followed by the addition of anhydrous sodium sulfate. The solution was filtered through Celite, concentrated and purified the concentrated by silica gel column chromatography to furnish the N2-(3,4-ethylenedioxyphenyl)-N4-[4-(2-hydroxy-1,1-dimethylethyl)phenyl]-5-fluoro-2,4-pyrimidinediamine. 1H NMR (DMSO-d6): δ 10.01 (br s, 1H), 9.6 (br s, 1H), 8.13 (d, 1H, J=4.7 Hz), 7.58 (d, 2H, J=8.2 Hz), 7.31 (d, 2H, J=8.8 Hz), 7.18 (d, 1H, J=2.3 Hz), 6.88 (dd, 1H, J=2.3 and 8.8 Hz), 6.73 (d, 1H, J=8.8 Hz), 4.21-4.19 (m, 4H), 3.56 (br s, 2H), 1.20 (s, 6H); LCMS: ret. time: 20.34 min.; purity: 98%; MS (m/e): 411 (MH+).

Workup

  1. customat 0° C.
  2. customReaction
  3. customwas quenched with methanol
  4. additiondiluted with ethylacetate
  5. additionfollowed by the addition of aqueous Rochelle's salt solution
  6. additionfollowed by the addition of anhydrous sodium sulfate
  7. filtrationThe solution was filtered through Celite
  8. concentrationconcentrated
  9. custompurified the
  10. concentrationconcentrated by silica gel column chromatography

Sources & evidence

ORD record
ord-033865cb220949739fe01ab303d36f52
Source dataset
uspto-grants-2014_10
Patent number
US08853397B2

Reaction notes

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