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

HRID 1977929Notes

Reaction equation

HRID 1977929 reaction equation
C([O-])(O)=O.[Na+].O.[C:7]1([OH:15])[CH:14]=[C:12]([CH3:13])[CH:11]=[C:9]([OH:10])[CH:8]=1.[Cl:16][C:17]1[CH:18]=[CH:19][C:20]([O:27][CH3:28])=[C:21]([S:23](Cl)(=[O:25])=[O:24])[CH:22]=1>C(OCCCC)CCC.O1CCCC1>[Cl:16][C:17]1[CH:18]=[CH:19][C:20]([O:27][CH3:28])=[C:21]([S:23]([O:10][C:9]2[CH:8]=[C:7]([OH:15])[CH:14]=[C:12]([CH3:13])[CH:11]=2)(=[O:24])=[O:25])[CH:22]=1

Participants

6

Reactant 3

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

Product 1

HCID 227225683-(5-Chloro-2-methoxyphenylsulfonyloxy)-5-methylphenolYield 295.3%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8909Butyl etherSolvent

Procedure

Saturated aqueous NaHCO3 (70 mL) was added to a solution of 5-chloro-2-methoxynenzensulfonyl 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 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 acetate 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) (7.81 (d, 1H, J=2.6 Hz), 7.55 (dd, 1H, J=8.9, 2.6 Hz), 7.02 (d, 1H, J=8.9 Hz), 6.53 (m, 2H), 6.41 (t, 1H, J=2.2 Hz), 3.99 (s, 3H), 2.24 (s, 3H). 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-5d4c0b191c1349f29c395a38e33f2a77
Source dataset
uspto-grants-2001_05
Patent number
US06235778B1

Reaction notes

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