Triphenylphosphine → Phosphoric acid dibenzyl ester 3-oxo-2,3-dihydro-7-oxa-1,2-diazabenzo[de]anthracen-10-ylmethyl ester

HRID 1091467Notes

Reaction equation

HRID 1091467 reaction equation
[OH: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]([O-])([O:31][CH2:32][C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1)([O:23][CH2:24][C:25]1[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=1)=[O:22].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.N(C(OC(C)C)=O)=NC(OC(C)C)=O>CN(C=O)C>[O:20]=[C:17]1[C:8]2[CH:9]=[CH:10][CH:11]=[C:12]3[O:13][C:14]4[CH:15]=[CH:16][C:3]([CH2:2][O:1][P:21](=[O:22])([O:31][CH2:32][C:33]5[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=5)[O:23][CH2:24][C:25]5[CH:30]=[CH:29][CH:28]=[CH:27][CH:26]=5)=[CH:4][C:5]=4[C:6]([C:7]=23)=[N:19][NH:18]1

Participants

6

Reactant 4

HCID 11776TriphenylphosphineHCID 75555Diisopropyl diazene-1,2-dicarboxylateHCID 4193600DibenzylphosphateHCID 1145979210-Hydroxymethyl-2H-7-oxa-1,2-diaza-benzo[de]anthracen-3-one

Product 1

HCID 11226277Phosphoric acid dibenzyl ester 3-oxo-2,3-dihydro-7-oxa-1,2-diazabenzo[de]anthracen-10-ylmethyl esterYield 40%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

To a solution of compound 57 (0.25 mmol) in anhydrous DMF was added dibenzyl phosphate (0.80 mmol) and triphenylphosphine (0.80 mmol). The reaction mixture was stirred while diisopropyl azodicarboxylate was added slowly. The reaction mixture was stirred at room temperature for 3 hours. Solvent was removed in vacuo. To the residue, 100 mL of ethyl acetate was added. The organic layer was washed with water and brine, then dried with MgSO4. The Solvents were removed to afford a yellow oil. The oil was re-crystallized in EtOAc/Hexanes to afford an off-white solid 60 in 40% yield. MS (ES+): 527; Mp: 223-225° C.; 1H-NMR (CDCl3, 400 MHz): 9.91 (s, 1H), 8.13 (d, J=2.0 Hz, 1H), 8.11 (dd, J=8.0 and 1.0 Hz, 1H), 7.85 (t, J=8.0 Hz, 1H), 7.59 (dd, J=8.0 and 1.0 Hz, 1H), 7.45 (dd, J=8.5 and 1.0 Hz, 1H), 7.36-7.26 (m, 11H), 5.08 (m, 6H). Anal. Calcd. for C29H23N2O6P.(0.15hydrazine): C, 65.56; H, 4.48; N, 6.06. Found: C, 65.55; H, 4.33; N, 6.09.

Workup

  1. additionwas added slowly
  2. customSolvent was removed in vacuo
  3. additionTo the residue, 100 mL of ethyl acetate was added
  4. washThe organic layer was washed with water and brine
  5. dry with materialdried with MgSO4
  6. customThe Solvents were removed
  7. customto afford a yellow oil
  8. customThe oil was re-crystallized in EtOAc/Hexanes

Sources & evidence

ORD record
ord-222a21086c6147d89e08d3208d87576c
Source dataset
uspto-grants-2012_03
Patent number
US08129382B2

Reaction notes

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