Diethyl Ether → HCID 45103998, compound

HRID 2172891Notes

Reaction equation

HRID 2172891 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.CCOCC>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

7

Reactant 4

HCID 3283Diethyl EtherHCID 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 ppt being the compound). The filtrate too contained some compound. Therefore it was extracted using chloroform and ethyl acetate. The ppt. obtained was dissolved in chloroform and methanol. Both the dissolved ppt. 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). Anal. Calculated (C15H14Cl2N4O. 0.25 (C2H5)2O): C, 54.02; H, 4.67; N, 15.74. Found: C, 54.14; H, 4.56; N, 15.69.

Workup

  1. customAfter this the POCl3 was evaporated
  2. filtrationThe aqueous mixture was filtered (the ppt
  3. extractionTherefore it was extracted
  4. customobtained
  5. extractionand 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-66145f4195a44e2cb5ac5557240efc41
Source dataset
uspto-grants-2015_06
Patent number
US09056869B2

Reaction notes

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