Dichloromethane → 1-tert-butyl 3-ethyl 4-(2-(7-methoxy-4-methyl-2-oxoquinolin-1(2H)-yl)ethyl)piperazine-1,3-dicarboxylate

HRID 39685

Reaction equation

HRID 39685 reaction equation
ClCCl.[CH3:4][O:5][C:6]1[CH:15]=[C:14]2[C:9]([C:10]([CH3:20])=[CH:11][C:12](=[O:19])[N:13]2[CH2:16][CH:17]=O)=[CH:8][CH:7]=1.[N:21]1([C:32]([O:34][C:35]([CH3:38])([CH3:37])[CH3:36])=[O:33])[CH2:26][CH2:25][NH:24][CH:23]([C:27]([O:29][CH2:30][CH3:31])=[O:28])[CH2:22]1.C(O[BH-](OC(=O)C)OC(=O)C)(=O)C.[Na+]>C(Cl)(Cl)Cl.O.C(O)(=O)C>[CH3:4][O:5][C:6]1[CH:15]=[C:14]2[C:9]([C:10]([CH3:20])=[CH:11][C:12](=[O:19])[N:13]2[CH2:16][CH2:17][N:24]2[CH2:25][CH2:26][N:21]([C:32]([O:34][C:35]([CH3:36])([CH3:37])[CH3:38])=[O:33])[CH2:22][CH:23]2[C:27]([O:29][CH2:30][CH3:31])=[O:28])=[CH:8][CH:7]=1

Participants

8

Reactant 4

HCID 6344DichloromethaneHCID 5049666Sodium triacetoxyborohydrideHCID 114026711-tert-Butyl 3-ethyl piperazine-1,3-dicarboxylateHCID 59397837(7-methoxy-4-methyl-2-oxoquinolin-1(2H)-yl)acetaldehyde

Product 1

HCID 675391071-tert-butyl 3-ethyl 4-(2-(7-methoxy-4-methyl-2-oxoquinolin-1(2H)-yl)ethyl)piperazine-1,3-dicarboxylate

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 6212ChloroformSolvent

Procedure

To 3 mL of a dichloromethane solution containing 0.10 g of (7-methoxy-4-methyl-2-oxoquinolin-1(2H)-yl)acetaldehyde, 0.12 g of 1-tert-butyl 3-ethyl piperazine-1,3-dicarboxylate, 30 μl of acetic acid and 0.14 g of sodium triacetoxyborohydride were added at room temperature, and the mixture was stirred at room temperature for 1 hour and 40 minutes. The reaction mixture was added with water and chloroform. The organic layer was separated, and the aqueous layer was extracted twice with chloroform. The organic layer and the extract were combined, the resultant solution was dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The residue thus obtained was purified by silica gel column chromatography [eluent; chloroform:acetone=100:1] to obtain a colorless foam, 1-tert-butyl 3-ethyl 4-(2-(7-methoxy-4-methyl-2-oxoquinolin-1(2H)-yl)ethyl)piperazine-1,3-dicarboxylate. (2) To 2.6 mL of a dichloromethane solution containing 1-tert-butyl 3-ethyl 4-(2-(7-methoxy-4-methyl-2-oxoquinolin-1(2H)-yl)ethyl)piperazine-1,3-dicarboxylate, 1.3 mL of trifluoroacetic acid was added, the mixture was stirred at room temperature for 2 hours, and the solvent was removed under reduced pressure. The residue thus obtained was added with ethyl acetate and water, and the resultant solution was adjusted to pH 1.0 with 6 mol/L hydrochloric acid. The aqueous layer was separated, and the organic layer was extracted twice with 20 mL of 0.1 mol/L hydrochloric acid. The aqueous layer and an extract were combined, thereto was added ethyl acetate, and the resultant solution was adjusted to pH 8.5 with a 5 mol/L aqueous sodium hydroxide solution. The organic layer was separated, and the aqueous layer was adjusted to pH 11.5 with a 5 mol/L aqueous sodium hydroxide solution, and extracted with ethyl acetate. The organic layer and the extract were combined, the resultant solution was washed with a saturated sodium chloride solution, and dried over anhydrous magnesium sulfate, and the solvent was removed under reduced pressure to obtain 89 mg of a colorless foam, ethyl 1-(2-(7-methoxy-4-methyl-2-oxoquinolin-1(2H)-yl)ethyl)piperazine-2-carboxylate.

Workup

  1. additionwere added at room temperature
  2. customThe organic layer was separated
  3. extractionthe aqueous layer was extracted twice with chloroform
  4. dry with materialthe resultant solution was dried over anhydrous magnesium sulfate
  5. customthe solvent was removed under reduced pressure
  6. customThe residue thus obtained
  7. customwas purified by silica gel column chromatography [eluent; chloroform:acetone=100:1]

Sources & evidence

ORD record
ord-b757d593767d41e8a0407ccacd6c4cdb
Source dataset
uspto-grants-2013_09
Patent number
US08524738B2

Linked notes

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