Nitric Acid → HCID 89525275, compound

HRID 1528180Notes

Reaction equation

HRID 1528180 reaction equation
[N+:1]([O-:4])(O)=[O:2].[OH:5][C:6]1[CH:11]=[CH:10][CH:9]=[CH:8][C:7]=1[S:12]([N:15]([CH3:17])[CH3:16])(=[O:14])=[O:13].O>C(O)(=O)C.[Cl-].[Na+].O>[OH:5][C:6]1[C:11]([N+:1]([O-:4])=[O:2])=[CH:10][CH:9]=[CH:8][C:7]=1[S:12]([N:15]([CH3:17])[CH3:16])(=[O:14])=[O:13]

Participants

6

Reactant 3

HCID 944Nitric AcidHCID 962WaterHCID 15526061HCID 15526061, compound

Product 1

HCID 89525275HCID 89525275, compoundYield 22%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 57417360Sodium chloride; waterSolvent

Procedure

2.24 ml (47.4 mmol, 1.3 eq) of fuming nitric acid at 90% were added, over the course of 15 minutes, to a mixture of 7.17 g (35.6 mmol, 1 eq) of 2-hydroxy-N,N-dimethylbenzenesulfonamide in 35.5 ml of acetic acid in a bath at 5° C. The reaction medium was then stirred at ambient temperature. After one and a half hours, the reaction medium was hydrolyzed with water and brine. The reaction medium was then extracted with a 4/1 ethyl acetate/heptane mixture (2×100 ml). The organic phases were combined, dried over anhydrous sodium sulfate, filtered and concentrated. The solid obtained (8.66 g) was combined with GUL1537-178 and was chromatographed on silica gel (prepacked column, eluent heptane/(ethyl acetate+1% methanol), from 20% to 65% of (ethyl acetate+1% methanol)). A fraction enriched in ortho isomer was isolated, that is to say 3.7 g of a yellow solid. This solid was recrystallized from 40 ml of ethanol. 1.93 g of product were obtained in the form of a pale yellow solid. Yield=20%.

Workup

  1. waitAfter one and a half hours
  2. extractionThe reaction medium was then extracted with a 4/1 ethyl acetate/heptane mixture (2×100 ml)
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe solid obtained (8.66 g)
  7. customwas chromatographed on silica gel (prepacked column, eluent heptane/(ethyl acetate+1% methanol), from 20% to 65% of (ethyl acetate+1% methanol))
  8. customwas isolated
  9. customThis solid was recrystallized from 40 ml of ethanol

Sources & evidence

ORD record
ord-4160b741ef21442da2173055ca45b7eb
Source dataset
uspto-grants-2015_07
Patent number
US09090596B2

Reaction notes

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