Formaldehyde → (+/-)-2-Methoxy-N-(7-methyl-4-oxo-2-pyrimidin-4-yl-4,5,6,7,8,9-hexahydro-1,4a,7-triaza-benzocyclohepten-9-yl)-nicotinamide

HRID 1890402Notes

Reaction equation

HRID 1890402 reaction equation
[CH3:1][O:2][C:3]1[N:29]=[CH:28][CH:27]=[CH:26][C:4]=1[C:5]([NH:7][CH:8]1[C:14]2=[N:15][C:16]([C:20]3[CH:25]=[CH:24][N:23]=[CH:22][N:21]=3)=[CH:17][C:18](=[O:19])[N:13]2[CH2:12][CH2:11][NH:10][CH2:9]1)=[O:6].C=O.[C:32](O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>ClC(Cl)C>[CH3:1][O:2][C:3]1[N:29]=[CH:28][CH:27]=[CH:26][C:4]=1[C:5]([NH:7][CH:8]1[C:14]2=[N:15][C:16]([C:20]3[CH:25]=[CH:24][N:23]=[CH:22][N:21]=3)=[CH:17][C:18](=[O:19])[N:13]2[CH2:12][CH2:11][N:10]([CH3:32])[CH2:9]1)=[O:6]

Participants

5

Reactant 3

HCID 712FormaldehydeHCID 5049666Sodium triacetoxyborohydrideHCID 68733346(+/-)-2-Methoxy-N-(4-oxo-2-pyrimidin-4-yl-4,5,6,7,8,9-hexahydro-1,4a,7-triaza-benzocyclohepten-9-yl)-nicotinamide

Product 1

HCID 68734236(+/-)-2-Methoxy-N-(7-methyl-4-oxo-2-pyrimidin-4-yl-4,5,6,7,8,9-hexahydro-1,4a,7-triaza-benzocyclohepten-9-yl)-nicotinamideYield 24.5%

Reagents, catalysts & solvents 1

HCID 63651,1-DichloroethaneSolvent

Procedure

To a solution of 0.055 g (0.14 mmol) of (+/−)-2-methoxy-N-(4-oxo-2-pyrimidin-4-yl-4,5,6,7,8,9-hexahydro-1,4a,7-triaza-benzocyclohepten-9-yl)-nicotinamide (example 3) in 3.00 mL of dichloroethane was added 0.050 mL (0.70 mmol) of formaldehyde (37% in water solution), 0.089 g (0.42 mmol) of sodium triacetoxyborohydride. The reaction mixture was stirred at room temperature for 12 hours. A solution of sodium hydroxyl (35%) was added and the mixture was extracted with dichloromethane, washed with a saturated aqueous solution of sodium chloride, dried over sodium sulfate and evaporated. The residue was chromatographed on silica gel eluting with a mixture of dichloromethane/methanol/aqueous ammonia solution (29%) in the proportions 90/10/1 to afford 0.014 g (24%) of pure product.

Workup

  1. extractionthe mixture was extracted with dichloromethane
  2. washwashed with a saturated aqueous solution of sodium chloride
  3. dry with materialdried over sodium sulfate
  4. customevaporated
  5. customThe residue was chromatographed on silica gel eluting with a mixture of dichloromethane/methanol/aqueous ammonia solution (29%) in the proportions 90/10/1

Sources & evidence

ORD record
ord-3e1567e48c594d27b2fd4ace2d845d6e
Source dataset
uspto-grants-2013_08
Patent number
US08507475B2

Reaction notes

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