Formaldehyde → HCID 57585127, compound

HRID 2077578Notes

Reaction equation

HRID 2077578 reaction equation
N[C:2]1[CH:3]=[C:4]([C:9]2[CH:21]=[CH:20][C:12]3[N:13]=[C:14]([NH:16][C:17](=[O:19])[CH3:18])[S:15][C:11]=3[CH:10]=2)[CH:5]=[N:6][C:7]=1[Cl:8].[BH4-].[Na+].C=O.OS(O)(=O)=O.[BH3-][C:32]#[N:33].[Na+].[C:35]([O-])([O-])=O.[Na+].[Na+]>C1COCC1>[Cl:8][C:7]1[N:6]=[CH:5][C:4]([C:9]2[CH:21]=[CH:20][C:12]3[N:13]=[C:14]([NH:16][C:17](=[O:19])[CH3:18])[S:15][C:11]=3[CH:10]=2)=[CH:3][C:2]=1[N:33]([CH3:32])[CH3:35]

Participants

8

Reactant 6

HCID 712Formaldehyde2×HCID 1118Sulfuric AcidHCID 10340Sodium CarbonateHCID 4311764Sodium borohydrideHCID 5003444Sodium cyanoborohydrideHCID 51355176HCID 51355176, compound

Product 1

HCID 57585127HCID 57585127, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A suspension of N-(6-(5-amino-6-chloropyridin-3-yl)benzo[d]thiazol-2-yl)acetamide (500 mg, 1568 μmol) and NaBH4 (500 mg, 13216 μmol) in THF (4 mL) was cooled with an ice bath. A cold mixture of formaldehyde (700 μL, 9325 μmol) and H2SO4 (3000 μl, 9000 μmol) was added slowly. More formaldehyde (700 μL, 9325 μmol) was added followed by the addition of NaCNBH3 (excess). The mixture was neutralized with Na2CO3 and the mixture was aged at 40° C. for 2 h. After standing overnight at rt, the mixture was filtered, washed with H2O, and air dried. The mixture was suspended in pyridine (10 mL) and was treated with HCl (conc., 20 mL). The mixture was filtered, the residue was washed with HCl (5 N). The filtrate was neutralized with NaOH (5N) and Na2CO3. The resulting slurry was aged overnight. The slurry was filtered, washed with H2O, and air dried. The solid was suspended in hot DMSO (10 mL), diluted with hot H2O (10 mL), and filtered. The solid was air dried over the weekend to give the product as a green powder (180 mg). MS (ESI, pos. ion) m/z: calc'd for C16H15ClN4OS: 346.0. found: 347.0. 1H NMR (400 MHz, DMSO-d6) δ ppm 2.22 (s, 3H) 2.86 (s, 6H) 7.74-7.89 (m, 3H) 8.38 (d, J=21.13 Hz, 2H) 12.43 (s, 1H).

Workup

  1. temperaturewas cooled with an ice bath
  2. additionwas added slowly
  3. waitAfter standing overnight at rt
  4. filtrationthe mixture was filtered
  5. washwashed with H2O, and air
  6. customdried
  7. additionwas treated with HCl (conc., 20 mL)
  8. filtrationThe mixture was filtered
  9. washthe residue was washed with HCl (5 N)
  10. waitThe resulting slurry was aged overnight
  11. filtrationThe slurry was filtered
  12. washwashed with H2O, and air
  13. customdried
  14. additiondiluted with hot H2O (10 mL)
  15. filtrationfiltered
  16. customdried over the weekend

Sources & evidence

ORD record
ord-2d2b8327d8f143f58590338b47fb91b7
Source dataset
uspto-grants-2011_04
Patent number
US07928140B2

Reaction notes

Loading…