Phosphorus oxychloride → HCID 45103998, compound

HRID 1485337Notes

Reaction equation

HRID 1485337 reaction equation
[Cl:1][C:2]1[CH:10]=[CH:9][CH:8]=[C:7]2[C:3]=1[C:4]1[C:14](=O)[NH:13][C:12]([NH:16][C:17](=[O:22])[C:18]([CH3:21])([CH3:20])[CH3:19])=[N:11][C:5]=1[NH:6]2.O=P(Cl)(Cl)[Cl:25].C(Cl)(Cl)Cl.CO>C(Cl)(Cl)Cl.CO>[Cl:25][C:14]1[C:4]2[C:3]3[C:7](=[CH:8][CH:9]=[CH:10][C:2]=3[Cl:1])[NH:6][C:5]=2[N:11]=[C:12]([NH:16][C:17](=[O:22])[C:18]([CH3:21])([CH3:20])[CH3:19])[N:13]=1

Participants

6

Reactant 3

HCID 24813Phosphorus oxychlorideHCID 21584188Chloroform methanolHCID 135916071HCID 135916071, compound

Product 1

HCID 45103998HCID 45103998, compoundYield 70%

Reagents, catalysts & solvents 2

HCID 887MethanolSolventHCID 6212ChloroformSolvent

Conditions

Temperature
115 °C

Procedure

To 9 (2 g, 6.274 mmol) was added 30 mL of POCl3 in a 250 mL round bottom flask. The reaction mixture was refluxed at 110-120° C. for 4 hours. After this the POCl3 was evaporated and the mixture was neutralized using NH4OH. The aqueous mixture was filtered (the precipitate being the compound). The filtrate also contained some compound. Therefore, it was extracted using chloroform and ethyl acetate. The precipitate obtained was dissolved in chloroform and methanol. Both the dissolved precipitate and extracted filtrate were dried using sodium sulfate overnight. To the solution was added silica, and solvent was removed under reduced pressure to provide a silica gel plug. The plug was transferred on top of a column packed with silica gel, twenty times the weight of plug, eluted with chloroform, 1% methanol in chloroform and 5% methanol in chloroform. Fractions containing the product 10 (TLC) were pooled and evaporated to give a solid. The overall yield was 70%. TLC Rf 0.86 (chloroform-methanol 5:1), m.p. 245.6-246.1° C., 1H NMR: δ 1.24 (s, 9H, pivaloyl); 7.37-7.63 (m, 3H, phenyl); 10.32 (s, 1H, 9-NH, exch); 12.96 (s, 1H, 2-NH, exch).

Workup

  1. customAfter this the POCl3 was evaporated
  2. filtrationThe aqueous mixture was filtered (the precipitate
  3. extractionTherefore, it was extracted
  4. customThe precipitate obtained
  5. extractionBoth the dissolved precipitate and extracted filtrate
  6. customwere dried
  7. customsodium sulfate overnight
  8. additionTo the solution was added silica, and solvent
  9. customwas removed under reduced pressure
  10. customto provide a silica gel plug
  11. washeluted with chloroform, 1% methanol in chloroform and 5% methanol in chloroform
  12. additionFractions containing the product 10 (TLC)
  13. customevaporated
  14. customto give a solid

Sources & evidence

ORD record
ord-e54a4931bf3147e083286eb4553d6e5d
Source dataset
uspto-grants-2016_08
Patent number
US09422297B2

Reaction notes

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