Diisobutylaluminum hydride → HCID 22060456, compound

HRID 1483517Notes

Reaction equation

HRID 1483517 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-c827abf32ca644539c6ee23cbfe55066
Source dataset
uspto-grants-2016_08
Patent number
US09416112B2

Reaction notes

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