Formaldehyde → HCID 86719386, compound

HRID 2175650Notes

Reaction equation

HRID 2175650 reaction equation
[NH2:1][C:2]1[CH:3]=[C:4]([N:8]2[C:12]3[N:13]=[CH:14][N:15]=[C:16]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:23])([CH3:22])[CH3:21])[C:11]=3[C:10]([C:25]3[CH:30]=[CH:29][C:28]([Cl:31])=[CH:27][CH:26]=3)=[C:9]2[Cl:32])[CH:5]=[CH:6][CH:7]=1.C=O.[BH3-][C:36]#N.[Na+]>C1COCC1>[Cl:32][C:9]1[N:8]([C:4]2[CH:5]=[CH:6][CH:7]=[C:2]([NH:1][CH3:36])[CH:3]=2)[C:12]2[N:13]=[CH:14][N:15]=[C:16]([NH:17][C:18](=[O:24])[O:19][C:20]([CH3:21])([CH3:22])[CH3:23])[C:11]=2[C:10]=1[C:25]1[CH:26]=[CH:27][C:28]([Cl:31])=[CH:29][CH:30]=1

Participants

5

Reactant 3

HCID 712FormaldehydeHCID 5003444Sodium cyanoborohydrideHCID 86719385HCID 86719385, compound

Product 1

HCID 86719386HCID 86719386, compoundYield 19%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A mixture of tert-butyl 7-(3-aminophenyl)-6-chloro-5-(4-chlorophenyl)-7H-pyrrolo[2,3-d]pyrimidin-4-ylcarbamate (21) (421 mg, 0.89 mmol), aqueous HCHO (109 mg, 1.34 mmol) and 4 Å MS (3.0 g) in dry THF (5.0 mL) was stirred at r.t. overnight. NaBH3CN (56 mg, 0.89 mmol) was added and stirred at r.t. for 1 hr before the reaction was quenched with sat. NaHCO3 solution (10.0 mL), and was extracted with DCM (20.0 mL×2). The combined organic phases was washed with brine, dried over Na2SO4 and concentrated. The crude product was purified by column chromatographic (silica gel, 0 to 40% EA in PE) to afford tert-butyl 6-chloro-5-(4-chlorophenyl)-7-(3-(methylamino)phenyl)-7H-pyrrolo[2,3-d]pyrimidin-4-ylcarbamate (22) (82 mg, 19% yield) as a yellow solid. LC-MS (ESI): m/z (M/M+2) 483.1/485.8.

Workup

  1. stirringstirred at r.t. for 1 hr before the reaction
  2. customwas quenched with sat. NaHCO3 solution (10.0 mL)
  3. extractionwas extracted with DCM (20.0 mL×2)
  4. washThe combined organic phases was washed with brine
  5. dry with materialdried over Na2SO4
  6. concentrationconcentrated
  7. customThe crude product was purified by column chromatographic (silica gel, 0 to 40% EA in PE)

Sources & evidence

ORD record
ord-26cf8aec39694469be14d204c5c6748c
Source dataset
uspto-grants-2015_06
Patent number
US09062058B2

Reaction notes

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