4-Toluenesulfonyl chloride → Toluene-4-sulfonic acid 1-methyl-3-nitro-2-oxo-1,2-dihydro-quinolin-4-yl ester

HRID 2244816Notes

Reaction equation

HRID 2244816 reaction equation
[S:1](Cl)([C:4]1[CH:10]=[CH:9][C:7]([CH3:8])=[CH:6][CH:5]=1)(=[O:3])=[O:2].[OH:12][C:13]1[C:22]2[C:17](=[CH:18][CH:19]=[CH:20][CH:21]=2)[N:16]([CH3:23])[C:15](=[O:24])[C:14]=1[N+:25]([O-:27])=[O:26].CCN(CC)CC>C(#N)C.CN(C1C=CN=CC=1)C>[CH3:23][N:16]1[C:17]2[C:22](=[CH:21][CH:20]=[CH:19][CH:18]=2)[C:13]([O:12][S:1]([C:4]2[CH:10]=[CH:9][C:7]([CH3:8])=[CH:6][CH:5]=2)(=[O:3])=[O:2])=[C:14]([N+:25]([O-:27])=[O:26])[C:15]1=[O:24]

Participants

6

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 8471TriethylamineHCID 546821234-Hydroxy-1-methyl-3-nitro-1,2-dihydroquinolin-2-one

Product 1

HCID 60145177Toluene-4-sulfonic acid 1-methyl-3-nitro-2-oxo-1,2-dihydro-quinolin-4-yl esterYield 75.5%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6342AcetonitrileSolvent2×

Conditions

Temperature
35 °C

Procedure

A solution of tosyl chloride (30.0 g, 160 mmol) in 100 mL of acetonitrile was added to a stirred solution of the 4-hydroxy-1-methyl-3-nitro-1H-quinolin-2-one (32.0 g, 145.0 mmol), Et3N (17.65 g, 174.4 mmol), and DMAP (0.178 g, 1.45 mmol) in 300 mL of MeCN at 0° C. After the addition was complete, the reaction mixture was heated at 35° C. for 3 h. After the solvent was evaporated under reduced pressure, water (35 mL) and CH2Cl2 (50 mL) were added to the residue. The resulting precipitate was removed by filtration, and the filtrate was extracted with CH2Cl2 (3×200 mL). The combined extracts were dried, filtered through a plug of SiO2, and concentrated. The resulting residue was combined with the solid isolated earlier, and was triturated with ether to give 41.0 g (75%) of toluene-4-sulfonic acid 1-methyl-3-nitro-2-oxo-1,2-dihydro-quinolin-4-yl ester. 1H-NMR (CDCl3): δ 8.16 (dd, 1H, J=7.6, 1.2 Hz), 7.90 (m, 2H), 7.79 (m, 1H), 7.44 (m, 4H), 3.79 (s, 3H), 2.51 (s, 3H). MS: calculated for C17H14N2O6S+H 375.1; found: 375.3.

Workup

  1. additionAfter the addition
  2. customAfter the solvent was evaporated under reduced pressure, water (35 mL) and CH2Cl2 (50 mL)
  3. additionwere added to the residue
  4. customThe resulting precipitate was removed by filtration
  5. extractionthe filtrate was extracted with CH2Cl2 (3×200 mL)
  6. customThe combined extracts were dried
  7. filtrationfiltered through a plug of SiO2
  8. concentrationconcentrated
  9. customisolated earlier
  10. customwas triturated with ether

Sources & evidence

ORD record
ord-8fbf0deacc2e4a67b4742cf050692fb3
Source dataset
uspto-grants-2010_03
Patent number
US07678909B1

Reaction notes

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