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Chemical Structure| 67472-44-0 Chemical Structure| 67472-44-0
Chemical Structure| 67472-44-0

4-(Hydroxymethyl)benzenesulfonamide

CAS No.: 67472-44-0

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Cat. No.: A691794 Purity: 95%

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Product Details of [ 67472-44-0 ]

CAS No. :67472-44-0
Formula : C7H9NO3S
M.W : 187.22
SMILES Code : O=S(C1=CC=C(CO)C=C1)(N)=O
MDL No. :MFCD00837254
InChI Key :UULCVOIRJRJPQS-UHFFFAOYSA-N
Pubchem ID :10081162

Safety of [ 67472-44-0 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H315-H319-H335
Precautionary Statements:P261-P264-P271-P280-P302+P352-P304+P340-P305+P351+P338-P312-P362-P403+P233-P501

Application In Synthesis of [ 67472-44-0 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 67472-44-0 ]

[ 67472-44-0 ] Synthesis Path-Downstream   1~4

  • 2
  • [ 67472-44-0 ]
  • [ 40724-47-8 ]
YieldReaction ConditionsOperation in experiment
Step 2: 4-bromomethyl-benzene-sulphonamide 4-hydroxymethyl-benzene-sulphonamide (0.105 mg, 0.56 mmoles) was dissolved in DCM (5 mL). Polymer supported triphenylphosphine (294 mg, 2.4 mmoles/g, 1.12 mmoles) was added, and the mixture was stirred with a shaker at room temperature for 10 minutes. CBr4 (557 mg, 1.68 mmoles) was then added, and stirring was continued for 3 hours. The supported reagent was removed by filtration, the solvent was evaporated, and the crude material was purified by flash chromatography (SiO2, petroleum ether/AcOEt 9/1) to yield the title compound as a light-yellow solid (70 mg). Alkylating agents K3 and K4 were synthesised as described in step 2 of this same Example 4, starting from the corresponding commercially available alcohol derivatives.
  • 3
  • [ 22808-73-7 ]
  • [ 67472-44-0 ]
YieldReaction ConditionsOperation in experiment
75% With hydrogenchloride; lithium borohydride; In tetrahydrofuran; methanol; Step 3 Preparation of 4-(hydroxymethyl)benzenesulfonamide To a solution of methyl [4-(aminosulfonyl)]benzoate (5.8 g, 27 mmol) (Step 2) in THF (400 ml), methanol (1.6 ml, 40 mmol) and lithium borohydride (20 ml, 2M solution in THF, 42 mmol) were added over 10 minutes. After heating at reflux for 3.5 hours, the reaction mixture was cooled and poured over ice containing 1N HCl (80 ml). The reaction mixture was extracted with ethyl acetate, dried (Na2 SO4), filtered and concentrated. The crude mixture was purified by chromatography (silica gel, hexane/ethyl acetate, 1/1) to give 4-(hydroxymethyl)benzenesulfonamide (3.8 g, 75%) as a white solid.
17% 4-Hvdroxymethyl-benzenesulfonamide; To a solution of 5.2 g 4-sulfamoyl-benzoic acid methyl ester in 100 ml. THF and 1.44 ml. MeOH, 0.77 g lithium borohydride was added portion-wise over a period of 10 minutes. The mixture was heated at reflux overnight, cooled to room temperature, and poured onto ice containig 100 ml. 1 N HCI. The mixture was extracted with EtOAc, and the organic layer was dried over MgSO4 and concentrated under reduced pressure. The residue was purified by automated flash chromatography (EtOAc/Hexane 1 :1 ) to give 0.75 gram (17%) of product. 1H NMR (400 MHz, DMSO-de) delta 4.57 (d, J=5.81 Hz, 1 H), 5.38 (t, J=5.81 Hz, 1 H), 7.48 (d, J=8.34 Hz, 2H), 7.78 (d, J=8.34 Hz, 2H).
  • 4
  • [ 67472-44-0 ]
  • [ 3240-35-5 ]
YieldReaction ConditionsOperation in experiment
83% With Dess-Martin periodane; In acetonitrile; at 80℃; for 2h; A mixture of 4-(hydroxymethyl)benzenesulfonamide (1.00 g, 5.35 mmol, 1.0 equiv) and Dess-Martin periodinane (3.40 g, 8.02 mmol, 1.5 equiv) in CH3CN (40 mL) was stirred at 80C for 2 hours. Then aq. NaHCCb solution and aq. Na2S2Cb solution were added. The mixture was filtered and the filtrate was concentrated. The residue was purified by flash chromatography on silica gel (eluted with PE/EtOAc = 1/1) to afford 4- formylbenzenesulfonamide as a white solid (820 mg, 83% yield). NMR (400 MHz, DMSO-de) d: 10.10 (s, 1 H), 8.10 (d, J = 8.4 Hz, 2 H), 8.03 (d, J = 8.4 Hz, 2 H), 7.60 (s, 2 H). LC-MS: m/z 186.0 (M+H)+
55% With piridinium dichromate; In tetrahydrofuran; for 2h;Molecular sieve; A round bottom flask was charged with 4-hydroxymethylbenzenesulfonamide (3. 7 5 gm 20 mmol). 40 g of activated molecular sieves wereadded, and then 150 mL THF. 37.6 g (0.1 mol) of PDC was then added, and the mixture was10 allowed to stir for 2 hours, following which time TLC in 1:1 acetone:DCM indicated completeconversion of starting material. The mixture was filtered through a plug of silica, and eluted withacetone. The solvents were removed under vacuum, and the desired material obtained by MPLCusing a 0 to 60% ethyl acetate gradient in hexanes, affording 36 (2.05 g, 55%). 1H NMR (300MHz, DMSO-d6) 8 ppm 10.09 (s, 1H), 8.20-7.93 (m, 4H), 7.61 (s, 2H).
53% With pyridinium chlorochromate; In dichloromethane; acetone; Step 4 Preparation of 4-(formyl)benzenesulfonamide To a solution of 4-(hydroxymethyl)benzenesulfonamide (Step 3) (3.75 g, 20 mmol) in a mixture of acetone (250 ml) and methylene chloride (250 ml), pyridinium chlorochromate (6.47 g, 30 mmol) was added. After stirring at room temperature for 5 hours, the reaction mixture was diluted with ether and filtered through a short silica gel column. The column was eluted with hexane/ethyl acetate, (1/1). The fractions containing the desired material were combined and concentrated to give a white solid (2.0 g, 53%): mp 104-106 C. Anal Calc'd. for C7 H7 NSO3: C, 45.40; H, 3.81; N, 7.56; S, 17.31. Found: C, 45.61; H, 3.59; N, 7.18; S, 16.27.
With pyridinium chlorochromate; In dichloromethane; at 0 - 20℃; for 2h; General procedure: To a solution of methyl hydroxide (1.0 equiv) in dichloromethane, pyridinium chlorochromate (1.5 equiv) was added at 0 C. The mixture stirred at room temperature for 2 h, filtered by celite, concentrated in vacuo and the residue was purified by silica gel column chromatography with hexane/EtOAc as eluent to afford a desired product.

 

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