Trifluoromethanesulfonic acid → Methyl 2-amino-4-(2-{4-[4-(2-methoxyphenyl)piperazin-1-yl]butane-1-sulfinyl}phenyl)-6-methyl-5-nitro-1,4-dihydropyridine-3-carboxylate

HRID 373766Notes

Reaction equation

HRID 373766 reaction equation
[CH3:1][O:2][C:3]([C:5]1[CH:10]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[S:17][CH2:18][CH2:19][CH2:20][CH2:21][N:22]2[CH2:27][CH2:26][N:25]([C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][C:29]=3[O:34][CH3:35])[CH2:24][CH2:23]2)[C:9]([N+:36]([O-:38])=[O:37])=[C:8]([CH3:39])[NH:7][C:6]=1[NH2:40])=[O:4].FC(F)(F)S(O)(=O)=[O:44].ClC1C=CC=C(C(OO)=O)C=1.C(=O)(O)[O-].[Na+]>ClCCl>[CH3:1][O:2][C:3]([C:5]1[CH:10]([C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=2[S:17]([CH2:18][CH2:19][CH2:20][CH2:21][N:22]2[CH2:27][CH2:26][N:25]([C:28]3[CH:33]=[CH:32][CH:31]=[CH:30][C:29]=3[O:34][CH3:35])[CH2:24][CH2:23]2)=[O:44])[C:9]([N+:36]([O-:38])=[O:37])=[C:8]([CH3:39])[NH:7][C:6]=1[NH2:40])=[O:4]

Participants

6

Reactant 4

HCID 62406Trifluoromethanesulfonic acidHCID 70297m-Chloroperbenzoic acidHCID 516892Sodium BicarbonateHCID 44210117HCID 44210117, compound

Product 1

HCID 183813Methyl 2-amino-4-(2-{4-[4-(2-methoxyphenyl)piperazin-1-yl]butane-1-sulfinyl}phenyl)-6-methyl-5-nitro-1,4-dihydropyridine-3-carboxylate

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-10 °C

Procedure

To a 4-neck 500 ml round-bottom flask fitted with an addition funnel, thermometer and mechanical stirrer under a nitrogen atmosphere, was added 5.00 g of 2-amino-1,4-dihydro-4-(2-{4-[4-(2-methoxyphenyl)-1-piperazinyl]-butylthio}phenyl)-6-methyl-5-nitro-3-pyridinecarboxylic acid methyl ester and 120 ml of dichloromethane, followed by 1.73 ml of trifluoromethanesulfonic acid. The reaction mixture was cooled to -10° C. with an ice/acetone bath, and 1.88 g of 80% m-chloroperbenzoic acid in 120 ml of dichloromethane was added dropwise, maintaining -5° to -10° C. The reaction was stirred for an additional 2 hr. at -10° C. after the addition was complete. The reaction mixture was poured into conc. sodium bicarbonate, and the reaction flask was rinsed with acetone. The organic layer was separated, dried over magnesium sulfate, filtered and concentrated to an orange oil. The product (Ex. No. 2, Table 1) was isolated after column chromatography on silica gel, eluting with 20% methanol in ethyl acetate as an orange foam, 2.8 g. 1H-NMR (CDCl3) ∂ 1.84-2.05(m,2H); 2.03-2.05(m,2H); 2.36(s,3H); 2.55(t,2H,J=7Hz); 2.71(br s,4H); 3.00-3.18(br s,6H); 3.61(s,3H); 3.85(s,3H); 5.76(s,1H); 6.70(br s,2H); 6.83-7.03(m,4H); 7.28-7.41(m,4H); 7.82-7.86(m,1H). Mass spectrum: 584 (M+1).

Workup

  1. customTo a 4-neck 500 ml round-bottom flask fitted with an addition funnel
  2. temperaturemaintaining -5° to -10° C
  3. additionat -10° C. after the addition
  4. washthe reaction flask was rinsed with acetone
  5. customThe organic layer was separated
  6. dry with materialdried over magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated to an orange oil
  9. custom2, Table 1) was isolated after column chromatography on silica gel
  10. washeluting with 20% methanol in ethyl acetate as an orange foam, 2.8 g

Sources & evidence

ORD record
ord-899871ac797c4755894e05455e457d09
Source dataset
uspto-grants-1992_11
Patent number
US05166148

Reaction notes

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