Chlorosulfonic acid → HCID 86761396, compound

HRID 906636Notes

Reaction equation

HRID 906636 reaction equation
Cl[S:2]([OH:5])(=[O:4])=[O:3].[N+:6]([C:9]1[CH:10]=[C:11]([CH:21]=[CH:22][CH:23]=1)[C:12]([NH:14][CH2:15][C:16]1[S:17][CH:18]=[CH:19][CH:20]=1)=[O:13])([O-:8])=[O:7].[OH-].[CH2:25]([N+:29]([CH2:38][CH2:39][CH2:40][CH3:41])([CH2:34][CH2:35][CH2:36][CH3:37])[CH2:30][CH2:31][CH2:32][CH3:33])[CH2:26][CH2:27][CH3:28]>C(Cl)Cl>[N+:6]([C:9]1[CH:10]=[C:11]([CH:21]=[CH:22][CH:23]=1)[C:12]([NH:14][CH2:15][C:16]1[S:17][C:18]([S:2]([O-:5])(=[O:4])=[O:3])=[CH:19][CH:20]=1)=[O:13])([O-:8])=[O:7].[CH2:38]([N+:29]([CH2:25][CH2:26][CH2:27][CH3:28])([CH2:30][CH2:31][CH2:32][CH3:33])[CH2:34][CH2:35][CH2:36][CH3:37])[CH2:39][CH2:40][CH3:41]

Participants

5

Reactant 3

HCID 24638Chlorosulfonic acidHCID 897652HCID 897652, compoundHCID 2723671Tetrabutylammonium Hydroxide

Product 1

HCID 86761396HCID 86761396, compoundYield 97.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Chlorosulfonic acid (5.62 mL, 84 mmol) was dissolved in 20 mL CH2Cl2 and added to a solution of 3-Nitro-N-(thien-2-ylmethyl)benzamide (11.0 g, 42 mmol) in 100 mL CH2Cl2 under vigorous stirring. A gummy solid was formed and the reaction mixture was stirred for 3 h. The reaction was quenched with ice, and ice cold NaHCO3 solution was added to reach pH8.5. The aqueous layer was washed twice with CH2Cl2. Tetrabutylammoniumhydroxide (40% in water) (32 mL, 50 mmol) was added to the aqueous layer, while a solid was formed. The precipitate was extracted into CH2Cl2 and the aqueous layer was washed 3× with CH2Cl2. The combined organic layers were dried over MgSO4 and evaporated to dryness to afford a slightly colored foam of Tetrabutylammonium 5-{[(3-Nitrobenzoyl)amino]methyl}thiophene-2-sulfonate (24 g, 97%). NMR spectra indicated pure compound, which was used for the following chlorination step.

Workup

  1. customA gummy solid was formed
  2. customThe reaction was quenched with ice, and ice cold NaHCO3 solution
  3. additionwas added
  4. washThe aqueous layer was washed twice with CH2Cl2
  5. customwas formed
  6. extractionThe precipitate was extracted into CH2Cl2
  7. washthe aqueous layer was washed 3× with CH2Cl2
  8. dry with materialThe combined organic layers were dried over MgSO4
  9. customevaporated to dryness

Sources & evidence

ORD record
ord-b9263903c8394208913f5a7feebb67cb
Source dataset
uspto-grants-2011_09
Patent number
US08012995B1

Reaction notes

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