Pyridine → 3-Acetoxy-9H-xanthen-9-ylideneadamantane

HRID 725704Notes

Reaction equation

HRID 725704 reaction equation
[OH:1][C:2]1[CH:3]=[CH:4][C:5]2[C:6](=[C:16]3[CH:23]4[CH2:24][CH:19]5[CH2:20][CH:21]([CH2:25][CH:17]3[CH2:18]5)[CH2:22]4)[C:7]3[C:12]([O:13][C:14]=2[CH:15]=1)=[CH:11][CH:10]=[CH:9][CH:8]=3.N1C=CC=CC=1.[C:32](Cl)(=[O:34])[CH3:33]>C(Cl)Cl>[C:32]([O:1][C:2]1[CH:3]=[CH:4][C:5]2[C:6](=[C:16]3[CH:23]4[CH2:24][CH:19]5[CH2:20][CH:21]([CH2:25][CH:17]3[CH2:18]5)[CH2:22]4)[C:7]3[C:12]([O:13][C:14]=2[CH:15]=1)=[CH:11][CH:10]=[CH:9][CH:8]=3)(=[O:34])[CH3:33]

Participants

5

Reactant 3

HCID 1049PyridineHCID 6367Acetyl chlorideHCID 146455733-Hydroxy-9H-xanthen-9-ylideneadamantane2×

Product 1

HCID 146455743-Acetoxy-9H-xanthen-9-ylideneadamantaneYield 89.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent3×

Procedure

Hydroxy alkene 5a (0.577 g, 1.5 mmol) was dissolved in 20 mL of CH2Cl2 with 1.25 mL (1.22 g, 15.5 mmol) of pyridine. Acetyl chloride (0.6 mL, 0.662 g, 8.4 mmol) was dissolved in 5 mL of CH2Cl2 and added dropwise to the solution with 5a. A precipitate formed immediately. After stirring for 2 hours, the solvent was removed to give a yellow-orange solid. This material was treated with 50 mL of CH2Cl2 to leave a white solid which was separated by filtration. The CH2Cl2 solution was then concentrated and chromatographed over silica with 5% ethyl acetate/hexane to give 0.502 g (77.2%) of 5c as a white solid: mp 162°-163° C.; 1H NMR (CDCl3 delta 1.80-2.05 (m, 12H), 2.265 (s, 3H), 3.45-3.55 (m, 2H), 6.833 (dd, 1H, J=8.38, 2.32 Hz), 6.961 (d, 1H, J=2.33 Hz), 7.072 (ddd, 1H, J=8.11, 5.45, 2.08 Hz), 7.12-7.28 (m, 4H); 13C NMR (CDCl3) delta 20.96, 27.78, 32.50, 36.88, 39.36, 110.08, 115.72, 116.41, 122.75, 124.38, 126.44, 126.90, 127.42, 127.68, 146.81, 149.24, 154.86, 155.48, 169.18. ##STR41##

Workup

  1. customA precipitate formed immediately
  2. customthe solvent was removed
  3. customto give a yellow-orange solid
  4. customto leave a white solid which
  5. customwas separated by filtration
  6. concentrationThe CH2Cl2 solution was then concentrated
  7. customchromatographed over silica with 5% ethyl acetate/hexane

Sources & evidence

ORD record
ord-3ff03d4e6a874fc1a7259c6fc9c3f2a6
Source dataset
uspto-grants-1998_01
Patent number
US05707559

Reaction notes

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