Methylamine → HCID 67216563, compound

HRID 1628001Notes

Reaction equation

HRID 1628001 reaction equation
[CH3:1][NH2:2].[Cl:3][C:4]1[C:9]([CH2:10][CH:11]=O)=[CH:8][N:7]=[C:6]2[N:13]([S:16]([C:19]3[CH:25]=[CH:24][C:22]([CH3:23])=[CH:21][CH:20]=3)(=[O:18])=[O:17])[CH:14]=[CH:15][C:5]=12.[BH-](OC(C)=O)(OC(C)=O)OC(C)=O.[Na+].[BH4-].[Na+]>ClCCCl>[Cl:3][C:4]1[C:9]([CH2:10][CH2:11][NH:2][CH3:1])=[CH:8][N:7]=[C:6]2[N:13]([S:16]([C:19]3[CH:25]=[CH:24][C:22]([CH3:23])=[CH:21][CH:20]=3)(=[O:18])=[O:17])[CH:14]=[CH:15][C:5]=12

Participants

6

Reactant 4

HCID 6329MethylamineHCID 4311764Sodium borohydrideHCID 5049666Sodium triacetoxyborohydrideHCID 58382334HCID 58382334, compound

Product 1

HCID 67216563HCID 67216563, compoundYield 44%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent

Procedure

Methylamine gas was bubbled into a solution of 2-(4-chloro-1-tosyl-1H-pyrrolo[2,3-b]pyridin-5-yl)acetaldehyde (1.45 g, 4.16 mmol) in DCE (50 mL) for about 10 min. NaBH(OAc)3 (1.69 g, 7.97 mmol) was added and the mixture was stirred at rt. After about 45 min, the mixture was concentrated under reduced pressure then dissolved in MeOH (25 mL) and treated with NaBH4 (0.236 g, 6.24 mmol). After about 10 min, the mixture was concentrated under reduced pressure then partitioned between DCM (50 mL), saturated aqueous NaHCO3 (20 mL) and water (30 mL). The layers were separated then the aqueous layer was extracted with DCM (20 mL). The organic layers were combined, dried over anhydrous MgSO4, filtered and concentrated in vacuo. The material was purified by preparative reverse phase HPLC (Table 2, Method i). The desired fractions were collected then most of the MeCN was removed under reduced pressure. The solution was basified with saturated aqueous NaHCO3 and the solids were collected by filtration to give 2-(4-chloro-1-tosyl-1H-pyrrolo[2,3-b]pyridin-5-yl)-N-methylethanamine (0.67 g, 44%): LC/MS (Table 2, Method a) Rt=1.88 min; MS m/z 364 (M+H)+.

Workup

  1. concentrationthe mixture was concentrated under reduced pressure
  2. dissolutionthen dissolved in MeOH (25 mL)
  3. waitAfter about 10 min
  4. concentrationthe mixture was concentrated under reduced pressure
  5. customthen partitioned between DCM (50 mL), saturated aqueous NaHCO3 (20 mL) and water (30 mL)
  6. customThe layers were separated
  7. extractionthe aqueous layer was extracted with DCM (20 mL)
  8. dry with materialdried over anhydrous MgSO4
  9. filtrationfiltered
  10. concentrationconcentrated in vacuo
  11. customThe material was purified by preparative reverse phase HPLC (Table 2, Method i)
  12. customThe desired fractions were collected
  13. custommost of the MeCN was removed under reduced pressure
  14. filtrationthe solids were collected by filtration

Sources & evidence

ORD record
ord-94920ba2b0434c918f62593024d38734
Source dataset
uspto-grants-2014_07
Patent number
US08785639B2

Reaction notes

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