Diethyl chlorophosphate → (3-Oxo-2,3-dihydro-7-oxa-1,2-diaza-benzo[de]anthracen-10-ylmethyl)-phosphoramidic acid diethyl ester

HRID 2353180Notes

Reaction equation

HRID 2353180 reaction equation
[NH2:1][CH2:2][C:3]1[CH:16]=[CH:15][C:14]2[O:13][C:12]3[C:7]4=[C:8]([C:17](=[O:20])[NH:18][N:19]=[C:6]4[C:5]=2[CH:4]=1)[CH:9]=[CH:10][CH:11]=3.[P:21](Cl)([O:26][CH2:27][CH3:28])([O:23][CH2:24][CH3:25])=[O:22]>CN(C=O)C>[CH2:24]([O:23][P:21]([NH:1][CH2:2][C:3]1[CH:16]=[CH:15][C:14]2[O:13][C:12]3[C:7]4=[C:8]([C:17](=[O:20])[NH:18][N:19]=[C:6]4[C:5]=2[CH:4]=1)[CH:9]=[CH:10][CH:11]=3)(=[O:22])[O:26][CH2:27][CH3:28])[CH3:25]

Participants

4

Reactant 2

HCID 13139Diethyl chlorophosphateHCID 1119635510-(Aminomethyl)[1]benzopyrano[4,3,2-de]phthalazin-3(2H)-one

Product 1

HCID 11350137(3-Oxo-2,3-dihydro-7-oxa-1,2-diaza-benzo[de]anthracen-10-ylmethyl)-phosphoramidic acid diethyl esterYield 50%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of compound 49 (0.5 mmol) in anhydrous DMF (20 mL) was added diethyl chlorophosphate (1.5 mmol). After 3 hours solution was concentrated in vacuo, and 50 mL of water was added. The aqueous layer was extracted with 30 mL of EtOAc twice. Organic layers were combined and washed with 30 mL of brine. Organic layer was dried with MgSO4. Solvent was removed to afford a white solid, which was recrystallized in 10% of EtOAc in hexanes to afford a white solid 54 in 50% yield. MS (ES−): 400; Mp: 222.3-224.5° C.; 1H-NMR (CDCl3, 400 MHz): 10.21 (s, 1H), 8.10 (d, J=2.5 Hz, 1H), 8.03 (d, J=7.5 Hz, 1H), 7.79 (t, J=8.0 Hz, 1H), 7.52 (d, J=8.0 Hz, 1H), 7.47 (dd, J=8.5 and 2.0 Hz, 1H), 7.22 (d, J=8.5 Hz, 1H), 4.12 (m, 6H), 1.32 (t, J=6.5 Hz, 6H); Anal. Calcd. for C19H20N3O5P.(0.3H2O): C, 56.10; H, 5.10; N, 10.33. Found: C, 56.00; H, 5.03; N, 10.13.

Workup

  1. concentrationAfter 3 hours solution was concentrated in vacuo, and 50 mL of water
  2. additionwas added
  3. extractionThe aqueous layer was extracted with 30 mL of EtOAc twice
  4. washwashed with 30 mL of brine
  5. dry with materialOrganic layer was dried with MgSO4
  6. customSolvent was removed
  7. customto afford a white solid, which
  8. customwas recrystallized in 10% of EtOAc in hexanes

Sources & evidence

ORD record
ord-d03f1ea16f4c434cae3c914d80e172b3
Source dataset
uspto-grants-2010_07
Patent number
US07750008B2

Reaction notes

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