Acetic Acid → HCID 89445250, compound

HRID 2173667Notes

Reaction equation

HRID 2173667 reaction equation
[CH3:1][C:2]1[N:7]=[C:6]2[S:8][C:9]3[C:13]([NH2:14])=[N:12][NH:11][C:10]=3[C:5]2=[C:4]([CH3:15])[CH:3]=1.[CH3:16][O:17][C:18]1[CH:25]=[CH:24][C:21]([CH:22]=O)=[CH:20][CH:19]=1.C(O)(=O)C.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+].[OH-].[Na+]>ClCCCl.C(Cl)Cl>[CH3:16][O:17][C:18]1[CH:25]=[CH:24][C:21]([CH2:22][NH:14][C:13]2[C:9]3[S:8][C:6]4[C:5]([C:10]=3[NH:11][N:12]=2)=[C:4]([CH3:15])[CH:3]=[C:2]([CH3:1])[N:7]=4)=[CH:20][CH:19]=1

Participants

8

Reactant 5

HCID 176Acetic AcidHCID 14798Sodium HydroxideHCID 312444-MethoxybenzaldehydeHCID 5049666Sodium triacetoxyborohydrideHCID 71516705HCID 71516705, compound

Product 1

HCID 89445250HCID 89445250, compoundYield 73.9%

Reagents, catalysts & solvents 2

HCID 111,2-DichloroethaneSolventHCID 6344DichloromethaneSolvent

Procedure

The 6,8-dimethyl-1H-pyrazolo[3′,4′:4,5]thieno[2,3-b]pyridin-3-amine (70 mg, 0.32 mmol) was stirred in DCE (3.2 mL). To this solution was added 4-methoxybenzaldehyde (0.12 mL, 0.96 mmol), acetic acid (0.040 mL, 0.64 mmol) and NaBH(AcO)3 (140 mg, 0.64 mmol). The resulting slurry was stirred for 1 hr, LC\MS indicates the reaction is nearly complete. The reaction was stirred another hour, then diluted with DCM (15 mL) and treated with aqueous 1N NaOH (12 mL). The aqueous layer was separated and extracted with DCM. The combined organic layers were dried over Na2SO4, and concentrated under vacuum to give 180 mg of crude residue. The residue was purified by reverse-phase HPLC to give 80 mg of the pure product as a yellow TFA salt. 1H NMR (400 MHz, DMSO-d6): δ ppm 7.30 (d, J=8.6 Hz, 2H), 7.11 (s, 1H), 6.85 (2H, J=8.6 Hz, 2H), 5.74 (s, 1H), 4.32 (s, 2H), 3.70 (s, 3H), 2.62 (s, 3H), 2.50 (s, 3H). LC/MS: RT=0.63 min., m/z=339.0 [M+H]+.

Workup

  1. stirringThe reaction was stirred another hour
  2. customThe aqueous layer was separated
  3. extractionextracted with DCM
  4. dry with materialThe combined organic layers were dried over Na2SO4
  5. concentrationconcentrated under vacuum
  6. customto give 180 mg of crude residue
  7. customThe residue was purified by reverse-phase HPLC

Sources & evidence

ORD record
ord-11e0d005c68943fb895f4622e064f29f
Source dataset
uspto-grants-2015_06
Patent number
US09056876B2

Reaction notes

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