Bromine → HCID 66780709, compound

HRID 1958063Notes

Reaction equation

HRID 1958063 reaction equation
[Cl:1][C:2]1[C:3]([CH3:27])=[C:4]([CH2:8][N:9]2[C:14]3[N:15]=[C:16]([N:18]4[CH2:23][CH2:22][O:21][CH2:20][CH2:19]4)[S:17][C:13]=3[C:12](=[O:24])[N:11]=[C:10]2[CH2:25][CH3:26])[CH:5]=[CH:6][CH:7]=1.C([O-])(=O)C.[Na+].[Br:33]Br>C(O)(=O)C.O>[Br:33][CH:25]([C:10]1[N:9]([CH2:8][C:4]2[CH:5]=[CH:6][CH:7]=[C:2]([Cl:1])[C:3]=2[CH3:27])[C:14]2[N:15]=[C:16]([N:18]3[CH2:19][CH2:20][O:21][CH2:22][CH2:23]3)[S:17][C:13]=2[C:12](=[O:24])[N:11]=1)[CH3:26]

Participants

6

Reactant 3

HCID 24408BromineHCID 517045Sodium AcetateHCID 49820305HCID 49820305, compound

Product 1

HCID 66780709HCID 66780709, compoundYield 92.2%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Procedure

In a 100 mL round bottom flask combined 4-[(3-chloro-2-methylphenyl)methyl]-5-ethyl-2-(4-morpholinyl)[1,3]thiazolo[4,5-d]pyrimidin-7(4H)-one (4.1 g, 10.13 mmol) (Example 75) and sodium acetate (1.246 g, 15.19 mmol) in acetic acid (30 mL). Bromine (0.782 mL, 15.19 mmol) in acetic acid (5 mL) was added dropwise over ˜3 min. The red colored reaction was stirred at room temperature for 16 hr. LC/MS indicated complete conversion to product. This reaction mixture was diluted with water (150 mL), producing a gummy yellow residue. The mixture was extracted with chloroform (100 mL), then concentrated to a thick yellow oil. This oil was triturated from ether (150 mL), to provide, after sonication a yellow solid that is consistent with 5-(1-bromoethyl)-4-[(3-chloro-2-methylphenyl)methyl]-2-(4-morpholinyl)[1,3]thiazolo[4,5-d]pyrimidin-7(4H)-one (4.52 g, 9.34 mmol, 92% yield). The proton NMR is consistent for the desired product. LC/MS m/z MH+=484 (theoretical), found=484.9, 1H NMR (400 MHz, CHLOROFORM-d) S ppm 1.97 (d, J=6.57 Hz, 3H) 2.51 (s, 3H) 3.52-3.64 (m, 4H) 3.71-3.84 (m, 4H) 4.53-4.65 (m, 1H) 5.43 (d, J=17.43 Hz, 1H) 5.95 (d, J=17.43 Hz, 1H) 6.38 (d, J=7.83 Hz, 1H) 7.06 (t, J=8.08 Hz, 1H) 7.34 (d, J=7.83 Hz, 1H)

Workup

  1. customIn a 100 mL round bottom flask combined
  2. customThe red colored reaction
  3. customproducing a gummy yellow residue
  4. extractionThe mixture was extracted with chloroform (100 mL)
  5. concentrationconcentrated to a thick yellow oil
  6. customThis oil was triturated from ether (150 mL)
  7. customto provide
  8. customafter sonication a yellow solid

Sources & evidence

ORD record
ord-cb8ac8526c134c0995b829b24a91b709
Source dataset
uspto-grants-2013_04
Patent number
US08410095B2

Reaction notes

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