Phosphorus oxychloride → HCID 46866702, compound

HRID 1520758Notes

Reaction equation

HRID 1520758 reaction equation
[CH3:1][O:2][C:3]1[C:4]([O:32][CH3:33])=[CH:5][C:6]2[C:15]3[C:14](=O)[NH:13][C:12]4[CH:17]=[CH:18][CH:19]=[CH:20][C:11]=4[C:10]=3[N:9]([CH2:21][CH2:22][CH2:23][N:24]3[CH2:29][CH2:28][O:27][CH2:26][CH2:25]3)[C:8](=[O:30])[C:7]=2[CH:31]=1.O=P(Cl)(Cl)[Cl:36].P(Cl)(Cl)(Cl)(Cl)Cl>>[Cl:36][C:14]1[N:13]=[C:12]2[CH:17]=[CH:18][CH:19]=[CH:20][C:11]2=[C:10]2[C:15]=1[C:6]1[CH:5]=[C:4]([O:32][CH3:33])[C:3]([O:2][CH3:1])=[CH:31][C:7]=1[C:8](=[O:30])[N:9]2[CH2:21][CH2:22][CH2:23][N:24]1[CH2:29][CH2:28][O:27][CH2:26][CH2:25]1

Participants

4

Reactant 3

HCID 24813Phosphorus oxychlorideHCID 24819Phosphorus pentachloride2×HCID 49856746HCID 49856746, compound

Product 1

HCID 46866702HCID 46866702, compoundYield 66%

Procedure

Precursor 29 (22.5 mg, 0.05 mmol) was mixed with POCl3 (3 mL) and phosphorus pentachloride (100 mg, 10 equiv) was added slowly at room temperature. Starting material dissolved upon PCl5 addition, forming a clear yellow solution. The reaction mixture was stirred for 1 h and then heated at reflux for 1.5 h. After disappearance of starting material, the reaction mixture was cooled to room temperature and concentrated under reduced pressure. The brown oily residue was dissolved completely in ice-cold water (3 mL) and concentrated ammonium hydroxide solution was added dropwise to neutral pH. The cloudy aqueous solution was extracted with ethyl acetate (3×30 mL). The combined extracts were washed with concentrated ammonium hydrochloride solution, dried with sodium sulfate and evaporated to dryness under reduced pressure to yield 32 as an amorphous solid (15 mg, 66%): mp 185-190° C. (dec.), IR (KBr) 1651, 1606 cm−1; 1H NMR (500 MHz, CDCl3) δ 8.52 (s, 1 H), 8.17 (d, J=8.5 Hz, 1 H), 7.95 (d, J=7.6 Hz, 1 H), 7.82 (t, J=7.6 Hz, 1 H), 7.77 (s, 1 H), 7.71 (t, J=7.4 Hz, 1 H), 4.56-4.28 (m, 2 H), 3.97 (s, 3 H), 3.96-3.88 (m, 5 H), 3.76 (t, J=12.0 Hz, 2 H), 3.42 (d, J=11.9 Hz, 2 H), 3.18 (s, 2 H), 3.05 (d, J=11.1 Hz, 2 H), 2.42 (s, 2 H); 13C NMR (126 MHz, CDCl3) δ 161.90, 152.44, 149.88, 145.75, 144.76, 144.57, 130.45, 127.92, 126.50, 125.47, 124.66, 119.34, 117.80, 110.25, 108.06, 107.89, 63.23, 55.91, 55.78, 53.12, 50.89, 48.68, 22.93; positive ESIMS m/z (rel intensity) 468/470 (MH+, 100/32), 381/383 (97/30). Anal. Calcd for C25H28Cl3N3O4.1.2H2O: C, 53.38; H, 5.45; N, 7.47. Found: C, 53.36; H, 5.45; N, 7.10.

Workup

  1. additionwas added slowly at room temperature
  2. customforming a clear yellow solution
  3. temperatureheated
  4. temperatureat reflux for 1.5 h
  5. concentrationconcentrated under reduced pressure
  6. dissolutionThe brown oily residue was dissolved completely in ice-cold water (3 mL)
  7. additionconcentrated ammonium hydroxide solution was added dropwise to neutral pH
  8. extractionThe cloudy aqueous solution was extracted with ethyl acetate (3×30 mL)
  9. washThe combined extracts were washed with concentrated ammonium hydrochloride solution
  10. dry with materialdried with sodium sulfate
  11. customevaporated to dryness under reduced pressure

Sources & evidence

ORD record
ord-69e8e5b111544151ab6c2a72a9b6044c
Source dataset
uspto-grants-2015_07
Patent number
US09073920B2

Reaction notes

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