Methylamine → HCID 67280509, compound

HRID 1693301Notes

Reaction equation

HRID 1693301 reaction equation
[C:1]([O:4][BH-](OC(=O)C)OC(=O)C)(=O)[CH3:2].[Na+].[CH3:15][O:16][C:17]1C(C)=[CH:21][N:20]=[C:19]([CH2:24][N:25]2[N:53]=[C:29]3[CH2:30][C:31](=O)[C:32]4[CH2:33][S:34][N:35]=[C:36]([N:37](C(OC(C)(C)C)=O)C(OC(C)(C)C)=O)[C:27]([C:28]=43)=[N:26]2)[C:18]=1[CH3:54].Cl[CH:56](Cl)[CH3:57].[CH3:59][NH2:60].[OH-].[Na+]>O1CCCC1.C(O)(=O)C.CO>[NH2:37][C:36]1[C:27]2[C:28]3[C:29](=[N:53][N:25]([CH2:24][C:19]4[C:18]([CH3:54])=[C:17]([O:16][CH3:15])[C:56]([CH3:57])=[CH:21][N:20]=4)[N:26]=2)[CH2:30][CH:31]([N:60]([CH3:59])[C:1](=[O:4])[CH3:2])[C:32]=3[CH2:33][S:34][N:35]=1

Participants

9

Reactant 5

HCID 6329MethylamineHCID 63651,1-DichloroethaneHCID 14798Sodium HydroxideHCID 5049666Sodium triacetoxyborohydrideHCID 67279997HCID 67279997, compound

Product 1

HCID 67280509HCID 67280509, compoundYield 79%

Reagents, catalysts & solvents 3

HCID 887MethanolCatalystHCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolvent

Procedure

Sodium triacetoxyborohydride (32 mg) was added to a mixture composed of di-tert-butyl {2-[(4-methoxy-3,5-dimethylpyridin-2-yl)methyl]-8-oxo-2,7,8,9-tetrahydro-6-thia-1,2,3,5-tetraazabenzo[cd]azulen-4-yl}imidodicarbonate of Example 40 (57 mg), dichloroethane (1 ml), a 2 N solution of methylamine in tetrahydrofuran (0.2 ml) and acetic acid (23 μl), and the mixture was stirred at room temperature overnight. Methanol (one drop) was added dropwise to the reaction mixture, and then a 0.2 N sodium hydroxide solution was added, followed by extraction with ethyl acetate. The organic layer was dried over anhydrous sodium sulfate and filtered, and then the filtrate was concentrated under reduced pressure. Dichloromethane (2 ml) was added to the resulting residue, and pyridine (24 μl) and acetyl chloride (14 μl) were added dropwise under ice-cooling. 4-Dimethylaminopyridine (1 mg) was added and the mixture was stirred under ice-cooling for 10 minutes and at room temperature for three hours. Water was added to the reaction mixture, followed by extraction with ethyl acetate. Then, the organic layer was dried over anhydrous sodium sulfate and filtered, and then the filtrate was concentrated under reduced pressure. The resulting residue was purified by silica gel thin-layer chromatography (ethyl acetate), and then the title compound (19 mg, 79%) was obtained as an oil in the same manner as in Example 2.

Workup

  1. extractionfollowed by extraction with ethyl acetate
  2. dry with materialThe organic layer was dried over anhydrous sodium sulfate
  3. filtrationfiltered
  4. concentrationthe filtrate was concentrated under reduced pressure
  5. additionDichloromethane (2 ml) was added to the resulting residue, and pyridine (24 μl) and acetyl chloride (14 μl)
  6. additionwere added dropwise under ice-
  7. temperaturecooling
  8. addition4-Dimethylaminopyridine (1 mg) was added
  9. additionWater was added to the reaction mixture
  10. extractionfollowed by extraction with ethyl acetate
  11. dry with materialThen, the organic layer was dried over anhydrous sodium sulfate
  12. filtrationfiltered
  13. concentrationthe filtrate was concentrated under reduced pressure
  14. customThe resulting residue was purified by silica gel thin-layer chromatography (ethyl acetate)

Sources & evidence

ORD record
ord-c59987caadd0405bbd33f24add3d491a
Source dataset
uspto-grants-2012_04
Patent number
US08158638B2

Reaction notes

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