Water → 2-Hydroxyxanthone

HRID 1275524Notes

Reaction equation

HRID 1275524 reaction equation
C[O:2][C:3]1[CH:16]=[CH:15][C:14]2[O:13][C:12]3[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=3)[CH2:6][C:5]=2[CH:4]=1.Cl.N1C=CC=CC=1.[OH2:24]>>[OH:2][C:3]1[CH:16]=[CH:15][C:14]2[O:13][C:12]3[C:7](=[CH:8][CH:9]=[CH:10][CH:11]=3)[C:6](=[O:24])[C:5]=2[CH:4]=1

Participants

4

Reactant 3

HCID 962WaterHCID 98591742-methoxy-9H-xantheneHCID 10176127Pyridinium chloride

Product 1

HCID 747082-Hydroxyxanthone

Procedure

A solid mixture of 2-methoxy-9H-xanthene 2 (3.09 g, 14.6 mmole) and pyridine hydrochloride (23.85 g, 206.4 mmole) was heated at 200-210° for 1.5 hrs. The resulting reaction mixture was cooled to about 80° and treated with water, while a white powder dropped out of solution. The suspended mixture was stirred at ambient temperature and then cooled to 0°. The solid was filtered on a Buchner funnel and washed with cold water. A large quantity of CH2Cl2 was needed to redissolve the crude product. The CH2Cl2 solution was washed with dilute HCl solution. The aqueous layer was extracted with CH2Cl2. The combined organic layers were dried over anhydrous Na2SO4. TLC showed a small by-product at the origin, but neither of the starting material nor the oxidation product, 2-hydroxy-9H-xanthene-9-one, was formed. The CH2Cl2 solution was filtered through a silica gel plug, the silica gel was flushed with 20% EtOAc-hexanes (100 ml). After concentration of the filtrate, the crude 2-hydroxy-9H-xanthene 3 (2.68 g, 93%) was collected as a slightly yellow powder: mp 137-139° C. 1H NMR (DMSO-d6): delta 9.18 (1H, s), 7.14-7.22 (2H, m), 6.97-7.03 (2H, m), 6.87 (1H, dd, J=7.3, 1.8 Hz), 6.57-6.62 (2H, m) and 3.94 (2H, s).

Workup

  1. temperaturewas heated at 200-210° for 1.5 hrs
  2. customThe resulting reaction mixture
  3. temperaturewas cooled to about 80°
  4. additiondropped out of solution
  5. temperaturecooled to 0°
  6. filtrationThe solid was filtered on a Buchner funnel
  7. washwashed with cold water
  8. dissolutionto redissolve the crude product
  9. washThe CH2Cl2 solution was washed with dilute HCl solution
  10. extractionThe aqueous layer was extracted with CH2Cl2
  11. dry with materialThe combined organic layers were dried over anhydrous Na2SO4

Sources & evidence

ORD record
ord-39d804edd2904b79955b70d0883ef475
Source dataset
uspto-grants-2000_12
Patent number
US06162610

Reaction notes

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