Sodium Bicarbonate → 3-(5-Chloro-2-methoxyphenylsulfonyloxy)-5-methylphenol

HRID 442912Notes

Reaction equation

HRID 442912 reaction equation
C([O-])(O)=O.[Na+].[Cl:6][C:7]1[CH:8]=[CH:9][C:10]([O:17][CH3:18])=[C:11]([S:13](Cl)(=[O:15])=[O:14])[CH:12]=1.O.[C:20]1([OH:28])[CH:27]=[C:25]([CH3:26])[CH:24]=[C:22]([OH:23])[CH:21]=1>C(OCCCC)CCC.O1CCCC1>[Cl:6][C:7]1[CH:8]=[CH:9][C:10]([O:17][CH3:18])=[C:11]([S:13]([O:23][C:22]2[CH:21]=[C:20]([OH:28])[CH:27]=[C:25]([CH3:26])[CH:24]=2)(=[O:15])=[O:14])[CH:12]=1

Participants

6

Reactant 3

HCID 516892Sodium BicarbonateHCID 27342725-Chloro-2-methoxybenzene-1-sulfonyl chloride2×HCID 3083941Resorcinol, 5-methyl-, monohydrate

Product 1

HCID 227225683-(5-Chloro-2-methoxyphenylsulfonyloxy)-5-methylphenolYield 349.1%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8909Butyl etherSolvent

Procedure

Saturated aqueous NaHCO3 (70 mL) was added to a solution of 5-chloro-2-methoxybenzenesulfonyl chloride (3.83 g, 15.9 mmol) and orcinol monohydrate (3.39 g, 23.9 mmol) in di-n-butyl ether (53 mL) and tetrahydrofuran (17 mL). The biphasic solution was mixed vigorously at 50° C. for 7 h and then at ambient temperature overnight. The reaction mixture was combined with that from a previous reaction (which used 4.53 g [18.8 mmol] of 5-chloro-2-methoxybenzenesulfonyl chloride), the layers were separated, and the aqueous layer was extracted with ethyl acetate (2×100 mL). The combined organic extracts were washed with brine (250 mL), dried over Na2SO4, filtered, and evaporated to give 18.25 g of a clear brown oil. The product was purified by flash column chromatography (1% to 4% ethyl acetete in dichloromethane) to give the title compound (9.86 g, 86%) as a pale yellow oil which crystallized upon standing. 1H-NMR (300 MHz, CDCl3) δ 7.81 (d, 1 H, J =2.6 Hz), 7.55 (dd, 1 H, J=2.6, 8.9 Hz), 7.02 (d, 1 H, J=8.9 Hz), 6.53 (m, 2H), 6.41 (t, 1 H, J=2.2 Hz), 3.99 (s, 3 H), 2.24 (s, 3 H). Mass spectrum (MALDI-TOF, α-cyano-4-hydroxycinnamic acid matrix) calcd. for C14H13ClO5S: 351.0 (M+Na). Found: 351.1.

Workup

  1. additionThe biphasic solution was mixed vigorously at 50° C. for 7 h
  2. customat ambient temperature
  3. customovernight
  4. customthe layers were separated
  5. extractionthe aqueous layer was extracted with ethyl acetate (2×100 mL)
  6. washThe combined organic extracts were washed with brine (250 mL)
  7. dry with materialdried over Na2SO4
  8. filtrationfiltered
  9. customevaporated

Sources & evidence

ORD record
ord-e50e35c5f8b7428d85191c682a2c5945
Source dataset
uspto-grants-1999_04
Patent number
US05891909

Reaction notes

Loading…