Diethyl Ether → HCID 15168439, compound

HRID 484412Notes

Reaction equation

HRID 484412 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:6]=[C:7]([Cl:9])[CH:8]=1)[NH2:5].[CH3:10][O:11][C:12]([C:14]#[C:15][C:16]([O:18][CH3:19])=[O:17])=[O:13].C(OCC)C>CO>[CH3:10][O:11][C:12](=[O:13])[CH:14]([NH:5][C:4]1[CH:3]=[C:2]([Cl:1])[CH:8]=[C:7]([Cl:9])[CH:6]=1)[CH2:15][C:16]([O:18][CH3:19])=[O:17]

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 122813,5-DichloroanilineHCID 12980Dimethyl acetylenedicarboxylate

Product 1

HCID 15168439HCID 15168439, compound

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Procedure

3,5-Dichloroaniline (104 g) and dimethylacetylene dicarboxylate (79 ml) were dissolved in dry methanol (100 ml) and heated under reflux for 14 h. On cooling a yellow solid crystallised out and this was collected by filtration. The mother liquors were concentrated in vacuo to leave a residue from which a second crop of product was obtained by recrystallisation from diethyl ether/60-80 petrol. The combined crops of material weighed 167.5 g (after drying at 40° C. under a pressure of 20 mmHg for 18 h). A portion of this material (105 g) was dissolved in ethyl acetate (1000 ml) and hydrogenated at 50 psi over 10% palladium on carbon catalyst (4 g) for 40 h. The catalyst was removed by filtration and the solvent evaporated under vacuum to leave a residue which was recrystallised from diethyl ether/hexane to give the title compound as a white crystalline solid (84.8 g, m.p. 66°-67° C.); δ (360 MHz, CDCl3 ) 2.88 (2H, m, CHBHC), 3.71 (3H, s, CH3), 3.78 (3H, s, CH3), 4.36 (1H, t, J=5.4 Hz, CHACHBHC), 4.71 (1H, br, s, NH), 6.51 (2H, d, J=1.8 Hz, 2-H and 6-H), 6.73 (1H, t, J=1.8 Hz, 4-H); m/e 305 (M+), 246 (100%, M-CO2CH2); Found C, 47.14; H, 4.27; N, 4.56. C12H13Cl2NO4 requires C, 47.08; H, 4.28; N, 4.58%.

Workup

  1. temperatureheated
  2. temperatureunder reflux for 14 h
  3. temperatureOn cooling a yellow solid
  4. customcrystallised out and
  5. filtrationthis was collected by filtration
  6. concentrationThe mother liquors were concentrated in vacuo
  7. customto leave a residue from which a second crop of product
  8. customafter drying at 40° C. under a pressure of 20 mmHg for 18 h)
  9. dissolutionA portion of this material (105 g) was dissolved in ethyl acetate (1000 ml) and hydrogenated at 50 psi over 10% palladium on carbon catalyst (4 g) for 40 h
  10. customThe catalyst was removed by filtration
  11. customthe solvent evaporated under vacuum
  12. customto leave a residue which
  13. customwas recrystallised from diethyl ether/hexane

Sources & evidence

ORD record
ord-cd8c9abc137340d896b8ea908ed59817
Source dataset
uspto-grants-1993_07
Patent number
US05231102

Reaction notes

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