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

HRID 1876294Notes

Reaction equation

HRID 1876294 reaction equation
Cl.[CH2:2]([O:4][C:5]1[CH:12]=[CH:11][C:8]([CH:9]=O)=[CH:7][C:6]=1[OH:13])[CH3:3].[SH:14][CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1[SH:22].C([O-])(O)=O.[Na+]>ClCCl>[S:22]1[C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][C:16]=2[CH2:15][S:14][CH:9]1[C:8]1[CH:11]=[CH:12][C:5]([O:4][CH2:2][CH3:3])=[C:6]([OH:13])[CH:7]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 756794-Ethoxy-3-hydroxybenzaldehydeHCID 516892Sodium BicarbonateHCID 52551392-(Mercaptomethyl)benzenethiol

Product 1

HCID 441372795-(4H-benzo[d][1,3]dithiin-2-yl)-2-ethoxyphenolYield 71.2%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

Hydrogen chloride gas was bubbled for three minutes at 22° C. through a solution of 4-ethoxy-3-hydroxybenzaldehyde (0.50 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 (0.65 g, 70%) as a cream colored solid. 1H NMR (300 MHz, CDCl3, ppm) δ 1.46 (t, J=7 Hz, 3H), 3.98 (s, 3H), 4.13 (q, J=7 Hz, 2H), 5.44 (s, 1H), 5.68 (br s, 1H), 6.80 (d, J=8 Hz, 1H), 6.99 (dd, J=8 Hz, J2=2 Hz, 1H), 7.13 (d, J=2 Hz, 1H), 7.15-7.35 (m, 4H); 13C NMR (75 MHz, CDCl3, ppm) δ 15.1, 34.4, 51.2, 64.9, 111.6, 114.6, 120.0, 126.2, 127.7, 128.6, 129.4, 132.2, 135.1, 135.9, 146.0, 146.2; MS calculated for C16H16O2S2-H 303 observed 303.

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-8b267b295b494d309e3e85dad87b7ce4
Source dataset
uspto-grants-2012_11
Patent number
US08309598B2

Reaction notes

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