Ethyl orthopropionate → HCID 69506738, compound

HRID 2366721Notes

Reaction equation

HRID 2366721 reaction equation
[NH2:1][C:2]1[CH:3]=[N:4][C:5]2[C:10]([C:11]=1[NH:12][CH2:13][C:14]([CH3:21])([CH3:20])[C:15]([O:17][CH2:18][CH3:19])=[O:16])=[CH:9][CH:8]=[CH:7][CH:6]=2.[C:22](OCC)(OCC)(OCC)[CH2:23][CH3:24].C(OC)(OC)(OC)CCC.C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1>>[CH2:23]([C:24]1[N:12]([CH2:13][C:14]([CH3:20])([CH3:21])[C:15]([O:17][CH2:18][CH3:19])=[O:16])[C:11]2[C:10]3[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=3[N:4]=[CH:3][C:2]=2[N:1]=1)[CH3:22]

Participants

5

Reactant 4

HCID 66995Ethyl orthopropionate2×HCID 1235121,1,1-TrimethoxybutaneHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 57447056HCID 57447056, compound

Product 1

HCID 69506738HCID 69506738, compound

Procedure

Ethyl 3-[(3-aminoquinolin-4-yl)amino]-2,2-dimethylpropanoate (see Example 26 Parts A through D, 3.6 g, 12 mmol) was treated according to a modification of the method described in Part B of Example 8 using triethyl orthopropionate in lieu of trimethyl orthobutyrate. Prior to the addition of triethyl orthopropionate (4.0 mL, 20 mmol) and pyridinium p-toluenesulfonate (0.030 g), the reaction was heated at reflux for 15 minutes. After the reaction was heated at reflux for three hours, it was concentrated under reduced pressure and found to be incomplete by 1H NMR. The oil was dissolved in toluene (100 mL), and concentrated sulfuric acid (one drop) was added. The reaction was heated at reflux for two hours and allowed to cool. Triethylamine (5 mL) was added, and the reaction was heated at reflux for two hours, allowed to cool to ambient temperature, washed with saturated aqueous sodium bicarbonate (2×35 mL), dried over potassium carbonate, filtered, and concentrated to provide 3.6 g of ethyl 3-(2-ethyl-1H-imidazo[4,5-c]quinolin-1-yl)-2,2-dimethylpropanoate as an oil.

Workup

  1. additionwas treated
  2. temperaturethe reaction was heated
  3. temperatureat reflux for 15 minutes
  4. temperatureAfter the reaction was heated
  5. temperatureat reflux for three hours
  6. concentrationit was concentrated under reduced pressure
  7. dissolutionThe oil was dissolved in toluene (100 mL)
  8. additionconcentrated sulfuric acid (one drop) was added
  9. temperatureThe reaction was heated
  10. temperatureat reflux for two hours
  11. temperatureto cool
  12. additionTriethylamine (5 mL) was added
  13. temperaturethe reaction was heated
  14. temperatureat reflux for two hours
  15. washwashed with saturated aqueous sodium bicarbonate (2×35 mL)
  16. dry with materialdried over potassium carbonate
  17. filtrationfiltered
  18. concentrationconcentrated

Sources & evidence

ORD record
ord-7e7a4e669d70415181ac473d2dc532ba
Source dataset
uspto-grants-2014_04
Patent number
US08697873B2

Reaction notes

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