Hydrochloric Acid → 5-(4H-benzo[d][1,3]dithiin-2-yl)-2,3-dimethoxyphenol

HRID 1876295Notes

Reaction equation

HRID 1876295 reaction equation
Cl.[OH:2][C:3]1[CH:4]=[C:5]([CH:8]=[C:9]([O:13][CH3:14])[C:10]=1[O:11][CH3:12])[CH:6]=O.[SH:15][CH2:16][C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][C:18]=1[SH:23].C([O-])(O)=O.[Na+]>ClCCl>[S:23]1[C:18]2[CH:19]=[CH:20][CH:21]=[CH:22][C:17]=2[CH2:16][S:15][CH:6]1[C:5]1[CH:8]=[C:9]([O:13][CH3:14])[C:10]([O:11][CH3:12])=[C:3]([OH:2])[CH:4]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 1415133,4-Dimethoxy-5-hydroxybenzaldehydeHCID 516892Sodium BicarbonateHCID 52551392-(Mercaptomethyl)benzenethiol

Product 1

HCID 577508895-(4H-benzo[d][1,3]dithiin-2-yl)-2,3-dimethoxyphenolYield 79.1%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Hydrogen chloride gas was bubbled for three minutes at 22° C. through a solution of 3-hydroxy-4,5-dimethoxybenzaldehyde (0.55 g, 3.0 mmol) and 2-(mercaptomethyl)benzenethiol (0.52 g, 3.3 mmol) in dichloromethane (15 ml). After an additional 15 min., the reaction mixture was poured into saturated NaHCO3 (50 ml) and extracted with dichloromethane (2×75 ml). The combined organic layer was washed with brine (30 ml), dried (Na2SO4), filtered and concentrated providing a crude solid. This solid was triturated with hexane and then purified by flash chromatography using a gradient of hexanes (100%) up to hexanes (70%:30%). Concentration of the product containing fractions provided the above subtitle compound (0.76 g, 78%) as a white solid. 1H NMR (300 MHz, CDCl3, ppm) δ 3.84 (s, 3H), 3.90 (s, 3H), 3.94 (d, J=15 Hz, 1H), 4.00 (d, J=15 Hz, 1H), 5.42 (s, 1H), 5.89 (br s, 1H), 6.63 (d, J=2 Hz, 1H), 6.78 (d, J=2 Hz, 1H), 7.15-7.36 (m, 4H); 13C NMR (75 MHz, CDCl3, ppm) δ 34.3, 51.5, 56.0, 61.0, 104.1, 108.2, 126.4, 127.7, 128.5, 129.6, 135.2, 135.3, 135.5, 135.7, 149.4, 152.5; MS calculated for C16H16O3S2-H 319 observed 319.

Workup

  1. extractionextracted with dichloromethane (2×75 ml)
  2. washThe combined organic layer was washed with brine (30 ml)
  3. dry with materialdried (Na2SO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customproviding a crude solid
  7. customThis solid was triturated with hexane
  8. custompurified by flash chromatography
  9. additionConcentration of the product containing fractions

Sources & evidence

ORD record
ord-6af6b7c3ef5b43e0abfdf6622caf7500
Source dataset
uspto-grants-2012_11
Patent number
US08309598B2

Reaction notes

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