Diisobutylaluminum hydride → HCID 22060456, compound

HRID 734018Notes

Reaction equation

HRID 734018 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-65aa795426ac44c68d7ca039274c7b95
Source dataset
uspto-grants-2009_09
Patent number
US07589200B2

Reaction notes

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