Resorcinol → 9-(chloromethyl)-9H-xanthene

HRID 993357Notes

Reaction equation

HRID 993357 reaction equation
[Cl:1][CH2:2][C:3]([C:5]1[CH:11]=[CH:10][C:8](O)=[CH:7][C:6]=1[OH:12])=O.[C:13]1([CH:20]=[CH:19][CH:18]=[C:16](O)[CH:15]=1)O>CS(O)(=O)=O>[Cl:1][CH2:2][CH:3]1[C:20]2[CH:19]=[CH:18][CH:16]=[CH:15][C:13]=2[O:12][C:6]2[C:5]1=[CH:11][CH:10]=[CH:8][CH:7]=2

Participants

4

Reactant 2

HCID 5054ResorcinolHCID 23846862-Chloro-1-(2,4-dihydroxyphenyl)ethan-1-one

Product 1

HCID 184103399-(chloromethyl)-9H-xantheneYield 84.2%

Reagents, catalysts & solvents 1

HCID 6395Methanesulfonic AcidSolvent

Conditions

Temperature
85 °C

Procedure

A mixture of 4.91 g (51.84 mmol) of chloroacetic acid, 4 mL (54.84 mmol) of thionyl chloride and one drop of DMF was stirred at 90° C. for 3 hours. The resulting solution was cooled and evaporated to remove excess thionyl chloride, hydrogen chloride and sulfur dioxide to yield crude chloroacetyl chloride as a colorless oil, pure enough to use in the next step without further purification. To a stirred suspension of 8.01 g (60.07 mmol) of anhydrous aluminum chloride in 10 mL of nitrobenzene were added 2 mL of chloroacetyl chloride and 2.37 g (21.52 mmol) of resorcinol at 0° C. The mixture was stirred at 0° C. for 10 minutes and at room temperature for 16 hours, poured into ice (ca. 20 mL), hydrolyzed by conc. HCl (10 mL), diluted with water (20 mL) and chloroform (50 mL) and separated. The organic layer was dried over MgSO4, evaporated and purified by column chromatography (75 g of SiO2, 20% ethyl acetate-hexane) to yield 2.57 g (13.77 mmol, 64.0% yield) of 4-(2-chloroacetyl)resorcinol. A mixture of 167.2 mg (0.896 mmol) of 4-(2-chloroacetyl)resorcinol and 109.0 mg (0.990 mmol) of resorcinol in methanesulfonic acid (0.5 mL) was stirred at 85° C. for 1 hour. To the resulting deep red solution, ice (ca. 10 mL) was added to precipitate a product as a black gummy material which eventually became reddish brown fine powder after scratching with a spatula. The precipitate was collected by filtration, washed with water and dried over P2O5 under vacuum to yield 196.6 mg (0.754 mmol, 84% yield) of 9-chloromethylxanthene as a reddish brown solid. 1H NMR (D2O+K2CO3) δ 7.66 (1H, d, J=9 Hz). 6.60 (1H, dd, J=9 & 2 Hz), 6.30 (1H, d, J=2 Hz), 4.82 (2H, s); MS (ES, positive) 261.4, 263.4; UV (KMOPS, pH 7.2) λmax (ε) 515 nm (41,200 M−1cm−1).

Workup

  1. customto precipitate a product as a black gummy material which eventually became reddish brown fine powder
  2. filtrationThe precipitate was collected by filtration
  3. washwashed with water
  4. dry with materialdried over P2O5 under vacuum

Sources & evidence

ORD record
ord-3ebb85f6583d490b9dfabd3452541185
Source dataset
uspto-grants-2002_10
Patent number
US06472541B2

Reaction notes

Loading…