Benzyl Alcohol → Dibenzyl 1,3-dioxo-4-phenyl-1,2,3,6-tetrahydropyrrolo[3,4-c]carbazol-9-yl phosphate

HRID 11157Notes

Reaction equation

HRID 11157 reaction equation
[OH:1][C:2]1[CH:14]=[CH:13][C:12]2[NH:11][C:10]3[CH:9]=[C:8]([C:15]4[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=4)[C:7]4[C:21](=[O:25])[NH:22][C:23](=[O:24])[C:6]=4[C:5]=3[C:4]=2[CH:3]=1.[P:26](Cl)(Cl)(Cl)=[O:27].[CH2:31]([OH:38])[C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1.C([O:42][CH2:43][CH3:44])(=O)C>N1C=CC=CC=1.Cl>[P:26]([O:1][C:2]1[CH:14]=[CH:13][C:12]2[NH:11][C:10]3[CH:9]=[C:8]([C:15]4[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=4)[C:7]4[C:21](=[O:25])[NH:22][C:23](=[O:24])[C:6]=4[C:5]=3[C:4]=2[CH:3]=1)([O:42][CH2:43][C:44]1[CH:13]=[CH:14][CH:2]=[CH:3][CH:4]=1)([O:38][CH2:31][C:32]1[CH:37]=[CH:36][CH:35]=[CH:34][CH:33]=1)=[O:27]

Participants

7

Reactant 4

HCID 244Benzyl AlcoholHCID 8857Ethyl AcetateHCID 24813Phosphorus oxychloride2×HCID 43694919-Hydroxy-4-phenylpyrrolo[3,4-C]carbazole-1,3(2H,6H)-dione

Product 1

HCID 21980748Dibenzyl 1,3-dioxo-4-phenyl-1,2,3,6-tetrahydropyrrolo[3,4-c]carbazol-9-yl phosphateYield 32%

Reagents, catalysts & solvents 2

HCID 313Hydrochloric AcidSolventHCID 1049PyridineSolvent

Procedure

To a solution of 9-hydroxy-4-phenylpyrrolo[3,4-c]carbazole-1,3(2H,6H)-dione (I; Ar=phenyl) (0.50 g, 1.52 mmol) in pyridine (30 mL) under nitrogen was added phosphorous oxychloride (140 □L, 1.52 mmol) dropwise. After 40 minutes stirring at room temperature a further portion of phosphorous oxychloride (40 □L) was added and then after another 20 minutes, benzyl alcohol (0.66 mL, 6.38 mmol) was added. After 3 hours the reaction mixture was diluted with 1N hydrochloric acid and extraction with ethyl acetate. The organic phase was dried, the drying agent was removed and the solution was concentrated to dryness, before being chromatographed on silica eluting with methanol/dichloromethane (3:97) to give the dibenzyl phosphate (336) (284 mg, 32%) as a pale yellow powder, mp 193–194° C. 1H NMR δ [(CD3)2SO] 12.12 (br s, 1H), 11.15 (br s, 1H), 8.81 (br s, 1H), 7.69 (s, 1H), 7.63 (m, 3H), 7.48–7.34 (m, 14H), 5.22 (d, JH-F=8.3 Hz, 4H). Found: C, 69.65; H, 4.37; N, 4.88; P, 5.26. C34H25N2O6P requires: C, 69.38; H, 4.28; N, 4.76; P, 5.26.

Workup

  1. additionwas added
  2. customThe organic phase was dried
  3. customthe drying agent was removed
  4. concentrationthe solution was concentrated to dryness
  5. custombefore being chromatographed on silica eluting with methanol/dichloromethane (3:97)

Sources & evidence

ORD record
ord-fbb86781c71a49fe91ef221d735a96d5
Source dataset
uspto-grants-2006_08
Patent number
US07094798B1

Reaction notes

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