Phosphorus pentachloride → Methyl 4-[1-(aminosulfonyl)-3-methoxy-3-oxopropyl]-3-bromobenzoate

HRID 724677Notes

Reaction equation

HRID 724677 reaction equation
[Br:1][C:2]1[CH:7]=[C:6]([C:8]([O:10][CH3:11])=[O:9])[CH:5]=[CH:4][C:3]=1[CH:12]([S:18]([OH:21])(=O)=[O:19])[CH2:13][C:14]([O:16][CH3:17])=[O:15].[N:22]1C=CC=CC=1.P(Cl)(Cl)(Cl)(Cl)Cl.[OH-].N>C(Cl)Cl>[NH2:22][S:18]([CH:12]([C:3]1[CH:4]=[CH:5][C:6]([C:8]([O:10][CH3:11])=[O:9])=[CH:7][C:2]=1[Br:1])[CH2:13][C:14]([O:16][CH3:17])=[O:15])(=[O:21])=[O:19]

Participants

5

Reactant 3

HCID 24819Phosphorus pentachlorideHCID 21862953Ammonia hydroxideHCID 866020801-[2-bromo-4-(methoxycarbonyl)phenyl]-3-methoxy-3-oxopropane-1-sulfonic Acid pyridine

Product 1

HCID 21878646Methyl 4-[1-(aminosulfonyl)-3-methoxy-3-oxopropyl]-3-bromobenzoateYield 63%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

1-[2-bromo-4-(methoxycarbonyl)phenyl]-3-methoxy-3-oxopropane-1-sulfonic acid—pyridine (1:1) (0.220 g, 0.478 mmol) was dissolved in methylene chloride (2 mL) at room temperature, and phosphorus pentachloride (0.199 g, 0.956 mmol) were added. The mixture was stirred overnight. The reaction solution was cannulated into a 2 mL ammonia hydroxide solution at 0° C. dropwise. After stirring for 1 h, the organic layer was isolated, aqueous layer was extracted with methylene chloride twice. The combined organic solutions were dried over sodium sulfate, filtered, concentrated. The residue was purified by preparative LCMS to afford product as slight yellow solid (114 mg, 63%). 1H NMR (400 MHz, CD3OD): δ 8.24 (d, J=1.5 Hz, 1H), 7.99 (dd, J=8.2, 1.5 Hz, 1H), 7.70 (d, J=8.2 Hz, 1H), 5.39 (dd, J=10.1, 4.9 Hz, 1H), 3.91 (s, 3H), 3.58 (s, 3H), 3.43 (dd, J=16.6, 4.9 Hz, 1H), 3.18 (dd, J=16.6, 10.1 Hz, 1H). LCMS found for C12H14BrNO6SNa (M+Na)+: m/z=401, 403.

Workup

  1. stirringAfter stirring for 1 h
  2. customthe organic layer was isolated
  3. extractionaqueous layer was extracted with methylene chloride twice
  4. dry with materialThe combined organic solutions were dried over sodium sulfate
  5. filtrationfiltered
  6. concentrationconcentrated
  7. customThe residue was purified by preparative LCMS

Sources & evidence

ORD record
ord-4fa5b2e886ab488e8683667fdb4f23ee
Source dataset
uspto-grants-2006_11
Patent number
US07141596B2

Reaction notes

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