Bromine → Methyl 3-((6-amino-8-bromo-2-(2-methoxyethoxy)-9H-purin-9-yl)methyl)benzoate

HRID 2197449Notes

Reaction equation

HRID 2197449 reaction equation
[NH2:1][C:2]1[N:10]=[C:9]([O:11][CH2:12][CH2:13][O:14][CH3:15])[N:8]=[C:7]2[C:3]=1[N:4]=[CH:5][N:6]2[CH2:16][C:17]1[CH:18]=[C:19]([CH:24]=[CH:25][CH:26]=1)[C:20]([O:22][CH3:23])=[O:21].C([O-])(=O)C.[Na+].[Br:32]Br>C(O)(=O)C>[NH2:1][C:2]1[N:10]=[C:9]([O:11][CH2:12][CH2:13][O:14][CH3:15])[N:8]=[C:7]2[C:3]=1[N:4]=[C:5]([Br:32])[N:6]2[CH2:16][C:17]1[CH:18]=[C:19]([CH:24]=[CH:25][CH:26]=1)[C:20]([O:22][CH3:23])=[O:21]

Participants

5

Reactant 3

HCID 24408BromineHCID 517045Sodium AcetateHCID 57816768Methyl 3-((6-amino-2-(2-methoxyethoxy)-9H-purin-9-yl)methyl)benzoate

Product 1

HCID 57816862Methyl 3-((6-amino-8-bromo-2-(2-methoxyethoxy)-9H-purin-9-yl)methyl)benzoateYield 67.1%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

A solution of Compound (4) (4.09 g, 11.45 mmol) and sodium acetate (14.26 g, 171.84 mmol) in acetic acid (50 mL) was cooled to 0° C. in an ice bath. Bromine (23.8 g, 148.93 mmol) was added dropwise by syringe. The reaction mixture was allowed to warm to room temperature and stirred overnight (16 hr), and subsequently quenched with saturated sodium sulfite solution. The quenched reaction mixture was extracted with dichloromethane (3×50 mL), dried over sodium sulfate and solvent evaporated to give Compound (5) as a yellow solid (3.35 g, 67% yield). 1H NMR (300 MHz, CDCl3) δ 3.44 (s, 3H), 3.77 (t, J=5.1, 9.9 Hz, 2H), 3.92 (s, 3H), 4.52 (t, J=4.8, 9.9 Hz, 2H), 5.35 (s, 2H), 7.41 (t, J=7.5, 13.5, Hz, 1H), 7.49 (d, J=7.8 Hz, 1H), 7.98 (d, J=7.8 Hz, 1H), 8.09 (s, 1H). LCMS: m/z for C17H18BrN5O4++H observed 437.0 and 438.0 at 3.62 minutes of a 6 minute run, gradient 5-95% CH3CN in H2O (C18 column).

Workup

  1. customsubsequently quenched with saturated sodium sulfite solution
  2. customThe quenched reaction mixture
  3. extractionwas extracted with dichloromethane (3×50 mL)
  4. dry with materialdried over sodium sulfate and solvent
  5. customevaporated

Sources & evidence

ORD record
ord-c51d166fa1254c7a9f5f3aedabc01636
Source dataset
uspto-grants-2012_12
Patent number
US08338593B2

Reaction notes

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