Phosphorus oxybromide → HCID 22595770, compound

HRID 456975Notes

Reaction equation

HRID 456975 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[N+:8]([O-])=[CH:7][C:6]([N+:13]([O-:15])=[O:14])=[C:5]2[C:16]([F:19])([F:18])[F:17].P(Br)(Br)([Br:22])=O>>[Br:22][C:7]1[C:6]([N+:13]([O-:15])=[O:14])=[C:5]([C:16]([F:19])([F:18])[F:17])[C:4]2[C:9](=[CH:10][CH:11]=[C:2]([Cl:1])[CH:3]=2)[N:8]=1

Participants

3

Reactant 2

HCID 24613Phosphorus oxybromideHCID 22595767HCID 22595767, compound

Product 1

HCID 22595770HCID 22595770, compoundYield 96.1%

Conditions

Temperature
100 °C

Procedure

A mixture of 3 (4.71 g, 16.1 mmol) and POBr3 (9.23 g, 32.2 mmol) were heated to 100° C. After 2 h, the reaction was cooled to rt and partitioned between EtOAc and H2O, adding ice when necessary. The mixture was stirred overnight to break up the solid materials. Et2O (100 mL) was added and the organic phase was removed. The remaining aqueous phase was extracted with EtOAc (3×100 mL). The combined organic phases were washed with brine, dried over MgSO4 and concentrated to afford 5.5 g (96%) of the desired product which was used without further purification. An analytically pure sample was obtained by recrystallization (EtOH) to provide a fluffy off-white solid, mp 120° C. Rf 0.61 (10% Ethyl acetate-hexane). 1H NMR (CDCl3, 300 MHz) δ8.16 (d, J=9.1 Hz, 1H), 8.16 (m, 1H), 7.92 (dd, J=2.2, 9.1 Hz, 1H); 19F NMR (CDCl3, 300 MHz) δ−57.63; 13C NMR (CDCl3, 75 MHz) δ146.50, 137.35, 134.25, 131.88, 131.32, 124.45, 124.40, 122.44, 121.96, 118.76; IR (KBr) υmax 1606, 1588, 1552, 1492, 1426, 1382, 1361, 1308, 1283, 1219, 1180, 1169, 1157, 1134, 1097, 1023, 960, 846, 823, 792, 693, 661, 632 cm−1.

Workup

  1. temperaturethe reaction was cooled to rt
  2. custompartitioned between EtOAc and H2O
  3. additionadding ice when necessary
  4. additionEt2O (100 mL) was added
  5. customthe organic phase was removed
  6. extractionThe remaining aqueous phase was extracted with EtOAc (3×100 mL)
  7. washThe combined organic phases were washed with brine
  8. dry with materialdried over MgSO4
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-31ccead4f28a4824a753dad6957c4007
Source dataset
uspto-grants-2007_03
Patent number
US07186830B2

Reaction notes

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