Phosphorus trichloride → HCID 68445122, compound

HRID 1886767Notes

Reaction equation

HRID 1886767 reaction equation
P(Cl)(Cl)[Cl:2].O[CH2:6][C:7]1[CH:8]=[CH:9][C:10]2[C:19]([N:20]=1)=[C:18]1[N:21]=[CH:22][CH:23]=[CH:24][C:17]1=[C:16]1[C:11]=2[N:12]=[C:13]([C:30]([O:32][CH2:33][CH3:34])=[O:31])[C:14]([C:25]([O:27][CH2:28][CH3:29])=[O:26])=[N:15]1>C(Cl)(Cl)Cl>[Cl:2][CH2:6][C:7]1[CH:8]=[CH:9][C:10]2[C:19]([N:20]=1)=[C:18]1[N:21]=[CH:22][CH:23]=[CH:24][C:17]1=[C:16]1[C:11]=2[N:12]=[C:13]([C:30]([O:32][CH2:33][CH3:34])=[O:31])[C:14]([C:25]([O:27][CH2:28][CH3:29])=[O:26])=[N:15]1

Participants

4

Reactant 2

HCID 24387Phosphorus trichlorideHCID 68446529HCID 68446529, compound

Product 1

HCID 68445122HCID 68445122, compoundYield 26%

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent

Procedure

Phosphorus trichloride (473 mg, 3.44 mmol) was added to a solution diethyl 7-(hydroxymethyl)dipyrido[3,2-f:2′,3′-h]quinoxaline-2,3-dicarboxylate (350 mg, 0.86 mmol) in CHCl3 (150 ml). The reaction mixture was heated under reflux for 6 h and allowed to cool down to room temperature afterwards. The reaction was quenched by addition of concentrated Na2CO3 solution (150 ml). The layers were separated and the water was extracted by CH2Cl2 (3×150 ml) and CHCl3 (1×50 ml). The organic layer was dried over K2CO3. The solvent was removed under reduced pressure to give the crude product. Purification was achieved by chromatography on alumina (gradient elution: CH2Cl2 to 2% CH3OH—CH2Cl2) The product was obtained as a yellow glass (95 mg, 0.22 mmol, 26%). 1H NMR (300 MHz, CDCl3): δ 1.45 (6H, t, J=7.2, OCH2CH3), 4.53 (4H, q, J=7.2, OCH2), 5.07 (2H, s, CH2Cl), 7.78 (1H, dd, J=8.1, 4.5, H11), 8.05 (1H, d, J=8.4, H6), 9.31 (1H, dd, J=4.5, 1.8, H10), 9.50 (1H, dd, J=8.1, 1.8, H12), 9.53 (1H, d, J=8.7, H5). 13C NMR (75 MHz, CDCl3): δ14.4 (CH3), 47.3 (CH2Cl), 63.2 (OCH2), 123.8 (C11), 124.6 (C6), 125.6 (q Ar), 126.6 (q Ar), 134.5 (C12), 135.7 (C5), 140.1 (q Ar), 140.4 (q Ar), 144.3 (q Ar), 144.4 (q Ar), 147.6 (q Ar), 148.1 (q Ar), 153.8 (C10), 161.0 (C7), 165.0 (CO), 165.1 (CO). m/z (ES+) 447 (MNa+).

Workup

  1. temperatureThe reaction mixture was heated
  2. temperatureunder reflux for 6 h
  3. customThe reaction was quenched by addition of concentrated Na2CO3 solution (150 ml)
  4. customThe layers were separated
  5. extractionthe water was extracted by CH2Cl2 (3×150 ml) and CHCl3 (1×50 ml)
  6. dry with materialThe organic layer was dried over K2CO3
  7. customThe solvent was removed under reduced pressure
  8. customto give the crude product
  9. customPurification

Sources & evidence

ORD record
ord-11e7d196a30f4e05ac494f1ada3792e5
Source dataset
uspto-grants-2013_08
Patent number
US08501398B2

Reaction notes

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