4-Toluenesulfonyl chloride → Toluene-4-sulfonic acid 5-nitro-3,4-dihydro-2H-benzo[1,4]oxazin-3-ylmethyl ester

HRID 896009Notes

Reaction equation

HRID 896009 reaction equation
[N+:1]([C:4]1[C:9]2[NH:10][CH:11]([CH2:14][OH:15])[CH2:12][O:13][C:8]=2[CH:7]=[CH:6][CH:5]=1)([O-:3])=[O:2].C(N(CC)C(C)C)(C)C.[C:25]1([CH3:35])[CH:30]=[CH:29][C:28]([S:31](Cl)(=[O:33])=[O:32])=[CH:27][CH:26]=1>C(Cl)Cl.CN(C1C=CN=CC=1)C>[N+:1]([C:4]1[C:9]2[NH:10][CH:11]([CH2:14][O:15][S:31]([C:28]3[CH:29]=[CH:30][C:25]([CH3:35])=[CH:26][CH:27]=3)(=[O:33])=[O:32])[CH2:12][O:13][C:8]=2[CH:7]=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

6

Reactant 3

HCID 73974-Toluenesulfonyl chlorideHCID 81531DiisopropylethylamineHCID 22349487(5-Nitro-3,4-dihydro-2H-benzo[1,4]oxazin-3-yl)-methanol

Product 1

HCID 20814149Toluene-4-sulfonic acid 5-nitro-3,4-dihydro-2H-benzo[1,4]oxazin-3-ylmethyl esterYield 93%

Reagents, catalysts & solvents 2

HCID 142844-(Dimethylamino)pyridineCatalystHCID 6344DichloromethaneSolvent2×

Procedure

(5-Nitro-3,4-dihydro-2H-benzo[1,4]oxazin-3-yl)-methanol (6.5 g, 31.0 mmole) was dissolved in methylene chloride (200 mL), N, N-diisopropylethylamine (10.8 mL, 62 mmole) and 4-DMAP (1.18 g) were added, followed by p-toluenesulfonyl chloride (12.85 g, 67.4 mmole) and the mixture stirred at room temperature under nitrogen overnight. The mixture was diluted with methylene chloride (100 mL), washed with HCl (1N, 200 mL), saturated sodium bicarbonate (200 mL), saturated sodium chloride (200 mL) and dried (Na2SO4). Filtration, evaporation in vacuum and column chromatography on silica gel with 1:1 hexane/methylene chloride as eluent gave 10.5 g (93%) of the title compound as a yellow solid. 1H NMR (DMSO-d6): δ 8.20 (d, 1H); 7.70 (d, 1H); 7.65 (dd, 1H); 7.40 (d, 2H); 7.05 (dd, 1H); 6.55 (dd, 1H); 4.10 (m, 5H); 2.40 (s, 3H).

Workup

  1. washwashed with HCl (1N, 200 mL), saturated sodium bicarbonate (200 mL), saturated sodium chloride (200 mL)
  2. dry with materialdried (Na2SO4)
  3. filtrationFiltration, evaporation in vacuum and column chromatography on silica gel with 1:1 hexane/methylene chloride as eluent

Sources & evidence

ORD record
ord-3d2a433a0b384bfaad1f169e5aa67048
Source dataset
uspto-grants-2005_07
Patent number
US06919334B2

Reaction notes

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